Organic compositions

ABSTRACT

The present invention provides a composition comprising (a) thermosetting component comprising: (1) optionally monomer of Formula I as set forth below and (2) at least one oligomer or polymer of Formula II as set forth below where E, Q, G, h, I, j, and w are as set forth below and (b) porogen that bonds to thermosetting component (a). Preferably, the porogen is selected from the group consisting of unsubstituted polynorbornene, substituted polynorbornene, polycaprolactone, unsubstituted polystyrene, substituted polystyrene, polyacenaphthylene homopolymer, and polyacenaphthylene copolymer. Preferably, the present compositions may be used as dielectric substrate in microchips, multichip modules, laminated circuit boards, or printed wiring boards.

BENEFIT OF PENDING APPLICATIONS

This application claims the benefit of pending commonly assignedprovisional patent applications 60/294864 filed May 30, 2001; 60/350187filed Jan. 15, 2002; 60/350557 filed Jan. 22, 2002; 60/353011 filed Jan.30, 2002; 60/376219 filed Apr. 29, 2002, and 60/378424 filed May 7,2002, incorporated herein in their entirety.

FIELD OF THE INVENTION

The present invention relates to semiconductor devices, and inparticular, to semiconductor devices having an organic low dielectricconstant material and processes for the manufacture thereof.

BACKGROUND OF THE INVENTION

In an effort to increase the performance and speed of semiconductordevices, semiconductor device manufacturers have sought to reduce thelinewidth and spacing of interconnects while minimizing the transmissionlosses and reducing the capacitative coupling of the interconnects. Oneway to diminish power consumption and reduce capacitance is bydecreasing the dielectric constant (also referred to as “k”) of theinsulating material, or dielectric, that separates the interconnects.Insulator materials having low dielectric constants are especiallydesirable, because they typically allow faster signal propagation,reduce capacitance and cross talk between conductor lines, and lowervoltages required to drive integrated circuits.

Since air has a dielectric constant of 1.0, a major goal is to reducethe dielectric constant of insulator materials down to a theoreticallimit of 1.0, and several methods are known in the art for reducing thedielectric constant of insulating materials. These techniques includeadding elements such as fluorine to the composition to reduce thedielectric constant of the bulk material. Other methods to reduce kinclude use of alternative dielectric material matrices. Anotherapproach is to introduce pores into the matrix.

Therefore, as interconnect linewidths decrease, concomitant decreases inthe dielectric constant of the insulating material are required toachieve the improved performance and speed desired of futuresemiconductor devices. For example, devices having interconnectlinewidths of 0.13 or 0.10 micron and below seek an insulating materialhaving a dielectric constant (k)<3.

Currently silicon dioxide (SiO₂) and modified versions of SiO₂, such asfluorinated silicon dioxide or fluorinated silicon glass (hereinafterFSG) are used. These oxides, which have a dielectric constant rangingfrom about 3.5-4.0, are commonly used as the dielectric in semiconductordevices. While SiO₂ and FSG have the mechanical and thermal stabilityneeded to withstand the thermal cycling and processing steps ofsemiconductor device manufacturing, materials having a lower dielectricconstant are desired in the industry.

Methods used to deposit dielectric materials may be divided into twocategories: spin-on deposition (hereinafter SOD) and chemical vapordeposition (hereinafter CVD). Several efforts to develop lowerdielectric constant materials include altering the chemical composition(organic, inorganic, blend of organic/inorganic) or changing thedielectric matrix (porous, non-porous). Table I summarizes thedevelopment of several materials having dielectric constants rangingfrom 2.0 to 3.5. (PE=plasma enhanced; HDP=high-density plasma) However,the dielectric materials and matrices disclosed in the publicationsshown in Table 1 fail to exhibit many of the combined physical andchemical properties desirable and even necessary for effectivedielectric materials, such as higher mechanical stability, high thermalstability, high glass transition temperature, high modulus or hardness,while at the same time still being able to be solvated, spun, ordeposited on to a substrate, wafer, or other surface. Therefore, it maybe useful to investigate other compounds and materials that may be usedas dielectric materials and layers, even though these compounds ormaterials may not be currently contemplated as dielectric materials intheir present form. TABLE 1 DEPOSITION DIELECTRIC MATERIAL METHODCONSTANT (k) REFERENCE Fluorinated silicon oxide PE-CVD; 3.3-3.5 U.S.Pat. No. No. 6,278,174 (SiOF) HDP-CVD Hydrogen SOD 2.0-2.5 U.S. patents4,756,977; 5,370,903; and Silsesquioxane (HSQ) 5,486,564; InternationalPatent Publication WO 00/40637; E.S. Moyer et at., “Ultra Low kSilsesquioxane Based Resins”, Concepts and Needs for Low DielectricConstant <0.15 μm Interconnect Materials: Now and the Next Millennium,Sponsored by the American Chemical Society, pages 128-146 (November14-17, 1999) Methyl Silsesquioxane SOD 2.4-2.7 U.S. Pat. No. 6,143,855(MSQ) Polyorganosilicon SOD 2.5-2.6 U.S. Pat. No. 6,225,238 FluorinatedAmorphous HDP-CVD 2.3 U.S. Pat. No. 5,900,290 Carbon (a-C:F)Benzocyclobutene SOD 2.4-2.7 U.S. Pat. No. 5,225,586 (BCB) PolyaryleneEther (PAE) SOD 2.4 U.S. patents 5,986,045; 5,874,516; and 5,658,994Parylene (N and F) CVD 2.4 U.S. Pat. No. 5,268,202 Polyphenylenes SOD2.6 U.S. patents 5,965,679 and 6,288,188B1; and Waeterloos et al.,“Integration Feasibility of Porous SiLK Semiconductor Dielectric”, Proc.Of the 2001 International Interconnect Tech. Conf., pp. 253-254 (2001).Thermosettable SOD 2.3 International Patent Publication WObenzocyclobutenes, 00/31183 polyarylenes, thermosettableperfluoroethylene monomer Poly(phenylquinoxaline), SOD 2.3-3.0 U.S.patents 5,776,990; 5,895,263; organic polysilica 6,107,357; and6,342,454; and US Patent Publication 2001/0040294 Organic polysilica SODNot reported U.S. Pat. No. 6,271,273 Organic and inorganic SOD 2.0-2.5U.S. Pat. No. 6,156,812 Materials Organic and inorganic SOD 2.0-2.3 U.S.Pat. No. 6,171,687 Materials Organic materials SOD Not reported U.S.Pat. No. 6,172,128 Organic SOD 2.12 U.S. Pat. No. 6,214,746Organosilsesquioxane CVD, SOD <3.9 WO 01/29052 Fluorosilsesquioxane CVD,SOD <3.9 WO 01/29141

Unfortunately, numerous organic SOD systems under development with adielectric constant between 2.0 and 3.5 suffer from certain drawbacks interms 5 of mechanical and thermal properties as described above;therefore a need exists in,the industry to develop improved processingand performance for dielectric films in this dielectric constant range.In addition, industry demands materials having demonstrated lowdielectric constant extendibility, i.e. capable of being reduced to aneven lower dielectric constant, e.g., from 2.7 to 2.5 to 2.2 to 2.0 andbelow.

Reichert and Mathias describe compounds and monomers that compriseadamantane molecules, which are in the class of cage-based molecules andare taught to be useful as diamond substitutes. (Polym, Prepr. (Am.Chem. Soc., Div. Polym. Chem.), 1993, Vol. 34 (1), pp. 495-6; Polym,Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), pp.144-5; Chem. Mater., 1993, Vol. 5 (1), pp. 4-5; Macromolecules, 1994,Vol. 27 (24), pp. 7030-7034; Macromolecules, 1994, Vol. 27 (24), pp.7015-7023; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1995, Vol.36 (1), pp. 741-742; 205^(th) ACS National Meeting, Conference Program,1993, pp. 312; Macromolecules, 1994, Vol. 27 (24), pp. 7024-9;Macromolecules, 1992, Vol. 25 (9), pp. 2294-306; Macromolecules, 1991,Vol. 24 (18), pp. 5232-3; Veronica R. Reichert, PhD Dissertation, 1994,Vol. 55-06B; ACS Symp. Ser.: Step-Growth Polymers for High-PerformanceMaterials, 1996, Vol. 624, pp. 197-207; Macromolecules, 2000, Vol. 33(10), pp. 3855-3859; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.),1999, Vol. 40 (2), pp. 620-621; Polym, Prepr. (Am. Chem. Soc., Div.Polym. Chem.), 1999, Vol. 40 (2), pp. 577-78; Macromolecules, 1997, Vol.30 (19), pp. 5970-5975; J. Polym. Sci, Part A: Polymer Chemistry, 1997,Vol. 35 (9), pp. 1743-1751; Polym, Prepr. (Am. Chem. Soc., Div. Polym.Chem.), 1996, Vol. 37 (2), pp. 243-244; Polym, Prepr. (Am. Chem. Soc.,Div. Polym. Chem.), 1996, Vol. 37 (1), pp. 551-552; J. Polym. Sci., PartA: Polymer Chemistry, 1996, Vol. 34 (3), pp. 397-402; Polym, Prepr. (Am.Chem. Soc., Div. Polym. Chem.), 1995, Vol. 36 (2), pp. 140-141; Polym,Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1992, Vol. 33 (2), pp.146-147; J. Appl. Polym. Sci., 1998, Vol. 68 (3), pp. 475-482). Theadamantane-based compounds and monomers described by Reichert andMathias are preferably used to form polymers with adamantane moleculesat the core of a thermoset. The compounds disclosed by Reichert andMathias in their studies, however, comprise only one isomer of theadamantane-based compound by design choice. Structure A shows thissymmetrical para- isomer1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane:

Structure A

In other words, Reichert and Mathias in their individual and joint workcontemplated a useful polymer comprising only one isomer form of thetarget adamantane-based monomer. A significant problem exists, however,when forming and processing polymers from the single isomer form(symmetrical “all-para” isomer)1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane of theadamantane-based monomer. According to the Reichert dissertation (supra)and Macromolecules, vol. 27, (pp. 7015-7034) (supra), the symmetricalall-para isomer 1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantane“was found to be soluble enough in chloroform that a ¹H NMR spectrumcould be obtained. However, acquisition times were found to beimpractical for obtaining a solution ¹³C NMR spectrum.” indicating thatthe all para isomer has low solubility. Thus, the Reichert symmetrical“all-para” isomer 1,3,5,7-tetrakis[4′-(phenylethynyl)phenyl]adamantaneis insoluble in standard organic solvents and therefore, would not beuseful in any application requiring solubility or solvent-basedprocessing, such as flow coating, spin coating, or dip coating.

In our commonly assigned pending patent application PCT/US01/22204 filedOct. 17, 2001 (claiming the benefit of our commonly assigned pendingpatent applications U.S. Ser. No. 09/545058 filed Apr. 7, 2000; U.S.Ser. No. 09/618945 filed Jul. 19, 2000; U.S. Ser. No. 09/897936 filedJul. 5, 2001; and U.S. Ser. No. 09/902924 filed Jul. 10, 2001; andInternational Publication WO 01/78110 published Oct. 18, 2001), wediscovered a composition comprising an isomeric thermosetting monomer ordimer mixture, wherein the mixture comprises at least one monomer ordimer having the structure correspondingly

wherein Z is selected from cage compound and silicon atom; R′₁, R′₂,R′₃, R′₄, R′₅, and R′₆ are independently selected from aryl, branchedaryl, and arylene ether; at least one of the aryl, the branched aryl,and the arylene ether has an ethynyl group; and R′₇ is aryl orsubstituted aryl. We also disclose methods for formation of thesethermosetting mixtures. This novel isomeric thermosetting monomer ordimer mixture is useful as a dielectric material in microelectronicsapplications and soluble in many solvents such as cyclohexanone. Thesedesirable properties make this isomeric thermosetting monomer or dimermixture ideal for film formation at thicknesses of about 0.1 μm to about1.0 μm.

We filed a patent application Serial No. 60/______ on even date herewiththat claims a porous version of the preceding isomeric mixture.

Our International Patent Publication WO 01/78110 published Oct. 18, 2001teaches in its background section that methods for introducing nanosizedvoids include physical blending or chemical grafting of thermostable orthermolabile portions. This publication's invention is that nanosizedvoids may be introduced into dielectric materials by using cagestructures such as adamantane or diamantane to achieve low dielectricconstant material and defines low dielectric constant materials ashaving a dielectric constant of less than 3.0. However, this publicationdoes not report any dielectric constant for its examples.

International Patent Publication WO 00/31183 teaches in its backgroundsection that although known porous thermoplastic materials hadacceptable dielectric constants, the pores tended to collapse duringsubsequent high temperature processing and thus, the art teaches awayfrom adding porosity to the cage structure that introduced nanosizedvoids in International Patent Publication WO 01/78110 published Oct. 18,2001. In addition, U.S. Pat. Nos. 5,776,990; 5,895,263; 6,107,357; and6,342,454 and US Publication 2001/0040294 teach that although dielectricconstants of 2.3-2.4 had been achieved at porosity levels less thanabout 20%, the pore content could not be further increased withoutcomprising the small domain sizes and/or the non-interconnectivity ofthe pore structure. Similarly, U.S. Pat. Nos. 6,271,273; 6,156,812;6,171,687; and 6,172,128 teach that the amount of the thermally labilemonomer unit is limited to amounts less than about 30% by volume becauseif more than about 30% by volume of the thermally labile monomer isused, the resulting dielectric material has cylindrical or lamellardomains, instead of pores or voids, which lead to interconnected orcollapsed structures upon removal, i.e., heating to degrade thethermally labile monomer units.

Although various methods are known in the art to lower the dielectricconstant of a material, these methods have disadvantages. Thus, there isstill a need in the semiconductor industry to a) provide improvedcompositions and methods to lower the dielectric constant of dielectriclayers; b) provide dielectric materials with improved properties, suchas thermal stability, glass transition temperature (T_(g)), modulus, andhardness; c) produce thermosetting compounds and dielectric materialsthat are capable of being solvated and spun-on to a wafer or layeredmaterial; and d) provide materials with demonstrated extendibility.

The present invention advantageously provides demonstrated extendibilityso that semiconductor device manufacturers can use the presentcompositions for numerous generations of microchips. Also, the presentinvention provides for bonding of a porogen to a thermosetting componentand thus, porogen movement is minimized and the possibility of poreaggregation is reduced.

SUMMARY OF THE INVENTION

In response to the need in the art and proceeding contrary to the wisdomin the art, we developed a composition comprising:

(a) thermosetting component comprising: (1) optionally monomer ofFormula I

and (2) at least one oligomer or polymer of Formula II

where E is a cage compound; each of Q is the same or different andselected from aryl, branched aryl, and substituted aryl wherein saidsubstituents include hydrogen, halogen, alkyl, aryl, substituted aryl,heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl,hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; G isaryl or substituted aryl where substituents include halogen and alkyl; his from 0 to 10; i is from 0 to 10; j is from 0 to 10; and w is 0 or 1;

(b) porogen that bonds to the thermosetting component (a).

We also discovered a method of lowering the dielectric constant of acomposition comprising: (a) thermosetting component comprising: (1 )optionally monomer of Formula I above and (2) at least one oligomer orpolymer of Formula II above where E, Q, G, h, I, and j are defined asabove; and

(b) adhesion promoter comprising compound having at leastbifunctionality wherein the bifunctionality may be the same or differentand the first functionality is capable of interacting with thethermosetting component (a) and the second functionality is capable ofinteracting with a substrate when the composition is applied to thesubstrate

comprising the steps of:

bonding porogen to the thermosetting component;

decomposing the bonded porogen; and

volatilizing the decomposed porogen whereby pores form in thecomposition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A through 1F illustrates how to make adamantane basedcompositions useful as the thermosetting component in the presentcompositions.

FIG. 2 illustrates one method for making diamantane based compositionsuseful as the thermosetting component in the present compositions.

FIGS. 3A through 3F illustrate another method for making diamantanebased compositions useful as the thermosetting component in the presentcompositions.

FIGS. 4 through 11 illustrate reaction schemes for covalently bondingthe thermosetting component to the porogen in the present compositions.

FIG. 12 illustrates the reaction scheme of Inventive Example 1.

FIG. 13 shows scanning electron microscopy pictures for the crosssection and surface of the film of Inventive Example 1.

FIG. 14 illustrates the reaction scheme of Inventive Example 2.

FIG. 15 shows scanning electron microscopy pictures for the crosssection and surface of the film of Inventive Example 2.

FIG. 16 illustrates the reaction scheme of Inventive Example 3.

DETAILED DESCRIPTION OF THE INVENTION

We filed a patent application 10/______ on even date herewith thatclaims a composition of a thermosetting component and a porogen whereinthe porogen does not have to bond to the thermosetting component.

Thermosetting Component:

The phrases “cage structure”, “cage molecule”, and “cage compound” asused herein are intended to be used interchangeably and refer to amolecule having at least eight atoms arranged such that at least onebridge covalently connects two or more atoms of a ring system. In otherwords, a cage structure, cage molecule, or cage compound comprises aplurality of rings formed by covalently bound atoms, wherein thestructure, molecule, or compound defines a volume, such that a pointlocated within the volume cannot leave the volume without passingthrough the ring. The bridge and/or the ring system may comprise one ormore heteroatoms, and may contain aromatic groups, partially cyclic oracyclic saturated hydrocarbon groups, or cyclic or acyclic unsaturatedhydrocarbon groups. Further contemplated cage structures includefullerenes, and crown ethers having at least one bridge. For example, anadamantane or diamantane is considered a cage structure, while anaphthalene or an aromatic spirocompound are not considered a cagestructure under the scope of this definition, because a naphthalene oran aromatic spirocompound do not have one, or more than one bridge andthus, do not fall within the description of the cage compound above.Cage compounds are preferably adamantane and diamantane and morepreferably adamantane.

The phrase “bridgehead carbon” as used herein refers to any cagestructure carbon bound to three other carbons. Thus, for example,adamantane has four bridgehead carbons while diamantane has eightbridgehead carbons.

Preferred dielectric material is thermosetting component disclosed andclaimed in our commonly assigned pending patent application 60/347195filed Jan. 8, 2002 and 60/______ filed on even date herewith, which areincorporated herein by reference in their entirety.

Preferably, the thermosetting component (a) comprises: (1) adamantanemonomer of Formula III

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

wherein h is from 0 to 10; i is from 0 to 10; j is from 0 to 10; each R₁in Formulae III, IV, V, and VI is the same or different and selectedfrom hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, arylether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl,hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; and each Y inFormulae III, IV, V, and VI is the same or different and selected fromhydrogen, alkyl, aryl, substituted aryl, or halogen.

Formulae II, IV, and VI represent random or irregular structures in thatany one of the units h, i, and j may or may not repeat numerous timesbefore another unit is present. Thus, the sequence of units in FormulaeII, IV, and VI above is random or irregular.

In the one embodiment, preferably the thermosetting component comprisesadamantane monomer of Formula III above and at least one adamantaneoligomer or polymer of Formula IV above where at least one of h, i, andj is at least 1. Preferably, the thermosetting component comprisesdiamantane monomer of Formula V above and at least one diamantaneoligomer or polymer of Formula VI above where at least one of h, i, andj is at least 1.

Preferably, the thermosetting component comprises adamantane monomer ofFormula III above and adamantane oligomer or polymer of Formula VIIbelow.

Preferably, the thermosetting component comprises diamantane monomer ofFormula V above and diamantane oligomer or polymer of Formula VIIIbelow.

Preferably, the thermosetting component comprises adamantane monomer ofFormula III above and adamantane dimer of Formula IX below.

Preferably, the thermosetting component comprises diamantane monomer ofFormula V above and diamantane dimer of Formula X below.

Preferably, the thermosetting component comprises adamantane monomer ofFormula III above and adamantane trimer of Formula XI below.

Preferably, the thermosetting component comprises diamantane monomer ofFormula V above and diamantane trimer of Formula XII below.

Preferably, the thermosetting component comprises adamantane monomer ofFormula III above, adamantane dimer of Formula IX above, and at leastone adamantane oligomer or polymer of Formula IV above where at leastone of h, i, and j is at least 1. Preferably, the thermosettingcomponent comprises diamantane monomer of Formula IV above, diamantanedimer of Formula X above, and at least one diamantane oligomer orpolymer of Formula VI above where at least one of h, i, and j is atleast 1.

Preferably, the thermosetting component comprises adamantane monomer ofFormula 11 above, adamantane dimer of Formula IX above, adamantanetrimer of Formula XI above, and at least one adamantane oligomer orpolymer of Formula IV above where at least one of i and j is at least 1.Preferably, the thermosetting component comprises diamantane monomer ofFormula V above, diamantane dimer of Formula X above, diamantane trimerof Formula XII above, and at least one diamantane oligomer or polymer ofFormula VI above where at least one of i and j is at least 1.

The thermosetting component comprises adamantane monomer of Formula IIIthat is a tetrasubstituted adamantane or a diamantane monomer of FormulaV that is a tetrasubstituted diamantane. The preferred monomer is theadamantane monomer of Formula III. The adamantane framework carries asubstituted aryl radical in each of positions 1, 3, 5, and 7. Thecompound with the Formula IV is an oligomer or polymer, linked viaunsubstituted and/or substituted aryl units, of the adamantane monomerof Formula III. The compound with the Formula VI is an oligomer orpolymer, linked via unsubstituted and/or substituted aryl units, of thediamantane monomer of Formula V. Generally, h, i, and j are wholenumbers from 0 to 10, preferably 0 to 5, and more preferably 0 to 2. Thesimplest adamantane oligomer is thus the dimer (h is 0, i is 0, and j is0 in Formula IV) as shown in Formula IX above, in which two adamantaneframeworks are linked via an unsubstituted or substituted aryl unit. Thesimplest diamantane oligomer is thus the dimer (h is 0, i is 0, and j is0 in Formula VI) as shown in Formula X above, in which two diamantaneframeworks are linked via an unsubstituted or substituted aryl unit.

In another embodiment, preferably the present thermosetting componentcomprises at least one adamantane oligomer or polymer of Formula IVabove where h is from 0 to 10, i is from 0 to 10, and j is from 0 to 10.Preferably, the present thermosetting component comprises at least onediamantane oligomer or polymer of Formula VI above where h is from 0 to10, i is from 0 to 10, and j is from 0 to 10.

Preferably, the present thermosetting component comprises at least oneadamantane oligomer or polymer of Formula IV above where h is 0 or 1, iis 0, and j is 0. This adamantane structure is shown as Formula VIIabove.

Preferably, the present thermosetting component comprises at least onediamantane oligomer or polymer of Formula VI above where h is 0 or 1, iis 0, and j is 0. This diamantane structure is shown as Formula VIIIabove.

Preferably, the thermosetting component comprises at least oneadamantane oligomer or polymer of Formula IV above where h is 0, i is 0,and j is 0. This adamantane dimer is shown as Formula IX above.

Preferably, the thermosetting component comprises at least onediamantane oligomer or polymer of Formula VI above where h is 0, i is 0,and j is 0. This diamantane dimer is shown as Formula X above.

Preferably, the thermosetting component comprises at least oneadamantane oligomer or polymer of Formula IV above where h is 1, i is 0,and j is 0. This adamantane trimer is as shown in Formula XI abpve.

Preferably, the thermosetting component (a) comprises at least onediamantane oligomer or polymer of Formula VI above where h is 1, i is 0,and j is 0. This diamantane trimer is as shown in Formula XII above.

Preferably, the thermosetting component comprises a mixture of at leastone adamantane oligomer or polymer of Formula IV above where h is 2, iis 0, and j is 0 (linear oligomer or polymer) and h is 0, i is 1, and jis 0 (branched oligomer or polymer). Thus, this composition comprises amixture of an adamantane linear tetramer as shown in Formula XIII below

and adamantane branched tetramer as shown Formula XIV below

Preferably, the thermosetting component comprises at least onediamantane oligomer or polymer of Formula VI above where h is 2, i is 0,and j is 0 (linear oligomer or polymer) and h is 0, i is 1, and j is 0(branched oligomer or polymer). Thus, the present composition comprisesdiamantane linear tetramer as shown in Formula XV below

and diamantane branched tetramer as shown Formula XVI below

Preferably, the thermosetting component comprises adamantane dimer ofFormula IX above and adamantane trimer of Formula XI above. Preferably,the thermosetting component comprises diamantane dimer of Formula Xabove and diamantane trimer of Formula XII above.

Preferably, the thermosetting component comprises adamantane dimer ofFormula IX above and at least one adamantane oligomer or polymer ofFormula IV above where h is 0, i is at least 1, and j is 0. Preferably,the thermosetting component comprises diamantane dimer of Formula Xabove and at least one diamantane oligomer or polymer of Formula VIabove where h is 0, i is at least 1, and j is 0.

In both embodiments, for Formulae I and II above, preferred Q groupsinclude aryl and aryl substituted with alkenyl and alkynyl groups andmore preferred Q groups include (phenylethynyl)phenyl,phenylethynyl(phenylethynyl)phenyl, and (phenylethynyl)phenylphenylmoiety. Preferred aryls for G include phenyl, biphenyl, and terphenyl.The more preferred G group is phenyl.

The individual radicals R₁ of the substituted ethynyl radical on thephenyl ring attached to the adamantane or diamantane ring of the typeR₁≡C— are in each case the same or different in Formulae III, IV, V, VI,VII, VIII, IX, X, XI, XII, XIII, XIV, XV, and XVI above. R₁ is selectedfrom hydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, arylether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl,hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl. Each R₁ may beunbranched or branched and unsubstituted or substituted and thesubstituents may be unbranched or branched. It is preferred that theradicals alkyl, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyalkenyl,and hydroxyalkynyl contain from about 2 to about 10 carbon atoms and theradicals aryl, aryl ether, and hydroxyaryl contain from about 6 to about18 carbon atoms. If R₁ stands for aryl, R₁ is preferably phenyl.Preferably, at least two of the R,C≡C groups on the phenyl groups aretwo different isomers. Examples of at least two different isomersinclude meta-, para-, and ortho-isomers. Preferably, the at least twodifferent isomers are meta- and para-isomers. In the preferred monomer,1,3,5,7-tetrakis[3′/4′-phenylethynyl)phenyl]adamantane (shown in FIG.1D), five isomers form: (1) para-, para-, para-, para-; (2) para-,para-, para-, meta-; (3) para-, para-, meta-, meta-; (4) para-, meta-,meta-, meta-; and (5) meta-, meta-, meta-, meta-.

Each Y of the phenyl rings in the Formulae III, IV, V, VI, VII, VIII,IX, X, XI, XII, XIII, XIV, XV, and XVI above is in each case the same ordifferent and selected from hydrogen, alkyl, aryl, substituted aryl, orhalogen. When Y is aryl, examples of aryl groups include phenyl orbiphenyl. Y is selected from preferably hydrogen, phenyl, and biphenyland more preferably hydrogen. Preferably, at least one of the phenylgroups between two bridgehead carbons of adamantane or diamantane existsas at least two different isomers. Examples of at least two differentisomers include meta-, para-, and ortho-isomers. Preferably, the atleast two isomers are meta- and para-isomers. In the most preferreddimer1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F), 14 isomers form as follows. Preferably, the phenylgroup located between the two bridgehead carbons of the adamantaneexists as meta- and para-isomers. For each of the two preceding isomers,seven isomers of the R₁C≡C groups on the phenyl groups exist as follows:(1) para-, para-, para-, para-, para-, para-; (2) para-, para-, para-,para-, para-, meta-; (3) para-, para-, para-, para-, meta-, meta-; (4)para-, para-, para-, meta-, meta-, meta-; (5) para-, para-, meta-,meta-, meta-, meta-; (6) para-, meta-, meta-, meta-, meta-, meta-; and(7) meta-, meta-, meta-, meta-, meta-, meta-.

In addition to the branched adamantane structure of Formula XIV above,it should be understood that Formula IV above when h is 0, i is 0, and jis 1 represents further branching as shown in Formula XVII below. Itshould be understood that branching may occur beyond that of the FormulaXVII structure because further branching of the pending adamantane unitsof the Formula XVII structure may also occur.

In addition to the branched diamantane structure of Formula XVI above,it should be understood that Formula VI above when h is 0, i is 0, and jis 1 represents further branching as shown in Formula XVIII below. Itshould be understood that branching may occur beyond that of the FormulaXVIII structure because further branching of the pending diamantaneunits of the Formula XVIII structure may also occur.

In thermosetting component, the monomer and oligomer or polymer contentsare determined by the gel permeation chromatography techniques set forthbelow in the Analytical Test Methods section. The present compositioncomprises the adamantane or diamantane monomer in a quantity of about 30to about 70 area-%, more preferably about 40 to about 60 area-% and evenmore preferably about 45 to about 55 area-% and the oligomer or polymerin a quantity of about 70 to about 30 area-%, more preferably about 60to about 40 area-%, and even more preferably about 55 to about 45area-%. Most preferably, the present composition comprises the monomer(1) in a quantity of approximately 50 area-% and the oligomer or polymer(2) in a quantity of approximately 50 area-%.

The Analytical Test Methods section sets forth two Gel PermeationChromatography Methods. Both provide similar results. One skilled in theart may elect to use the second method in that it yields additionaldetail on the dimer and trimer.

In general, the quantity ratio of the adamantane or diamantane monomer(1) to oligomer or polymer (2) can be set in a desired manner, e.g. byaltering the molar ratio of the starting components during thepreparation of the composition according to the invention, by adjustingreaction conditions, and by altering the ratio of nonsolvent to solventduring precipitation/isolation steps.

A preferred process for preparing the thermosetting component (a)comprises the following steps.

In step (A), adamantane or diamantane is reacted with halogeno benzenecompound of Formula XIX

where W is halogen,to form a mixture which if adamantane is used, comprises at least onemonomer of Formula XX

and at least one oligomer or polymer of Formula XXI where h is from 0 to10, i is from 0 to 10, and j is from 0 to 10

or if diamantane is used, comprises at least one monomer of Formula XXII

and at least one oligomer or polymer of Formula XXIII where h is from 0to 10, i is from 0 to 10, and j is from 0 to 10

It should be understood to those skilled in the art that reaction mayoccur on diamantane at bridgehead carbons other than those indicated inFormulae XXII and XXIII above.

In step (B), the mixture resulting from step (A) is reacted withterminal alkyne of the formula R₁C≡CH. Preferably, the present processforms compositions of Formulae III and IV or V and VI above.

In step (A), adamantane or diamantane is reacted with halogeno benzenecompound with the Formula XIX. In addition to the halogen radical W andthe previously described radical Y, the halogeno benzene compound canalso contain further substituents.

The halogeno benzene compound is preferably selected from bromobenzene,dibromobenzene, and iodobenzene. Bromobenzene and/or dibromobenzene arepreferred, bromobenzene being even more preferred.

The reaction of adamantane or diamantane with the halogeno benzenecompound (step (A)) takes place preferably through Friedel-Craftsreaction in the presence of a Lewis acid catalyst. Although allcustomary Lewis acid catalysts may be used, it is preferred that theLewis acid catalyst contains at least one compound selected fromaluminum(III) chloride (AlCl₃), aluminum(III) bromide (AlBr₃), andaluminum (III) iodide (AlI₃). Aluminum(III) chloride (AlCl₃) is mostpreferred. Despite the greater Lewis acidity of aluminum(III) bromide,its use is generally less preferred, because it has a low sublimationpoint of only 90° C. and is thus much more difficult to handle on anindustrial scale than e.g. aluminum(III) chloride.

In a further preferred version, the Friedel-Crafts reaction is carriedout in the presence of a second catalyst component. The second catalystcomponent preferably contains at least one compound selected fromtertiary halogen alkane with 4 to 20 carbon atoms, tertiary alkanol with4 to 20 carbon atoms, secondary and tertiary olefin with 4 to 20 carbonatoms and tertiary halogen alkyl aryl compound. In particular, thesecond catalyst component contains at least one compound selected from2-bromo-2-methylpropane (tert.-butyl bromide), 2-chloro-2-methylpropane(tert.-butyl chloride), 2-methyl-2-propanol (tert.-butyl alcohol),isobutene, 2-bromopropane, and tert.-butylbromobenzene, with2-bromo-2-methylpropane (tert.-butyl bromide) being most preferred.Overall, compounds whose alkyl groups include 5 or more carbon atoms areless suitable, as solid constituents precipitate out of the reactionsolution at the end of the reaction.

It is most preferred that the Lewis acid catalyst is aluminum(III)chloride (AlCl₃) and the second catalyst component is2-bromo-2-methylpropane (tert.-butyl bromide) ortert.-butylbromobenzene.

The preferable procedure for carrying out the Friedel-Crafts reaction isthat adamantane or diamantane, halogeno benzene compound (e.g.bromobenzene), and Lewis acid catalyst (e.g. aluminium chloride) aremixed and heated at a temperature of 30° C. to 50° C., preferably 35° C.to 45° C. and in particular 40° C. At temperatures lower than 30° C.,the reaction is not completed, i.e. a higher proportion oftri-substituted adamantane forms for example. In principle it isconceivable to use even higher temperatures than those given above (e.g.60° C.), but this leads in an undesirable manner to a higher proportionof non-halogenated aromatic material (e.g. benzene) in the reactionmixture of step (A). The second component of the catalyst system, saytert.-butyl bromide, is then added to the above reaction solutiongenerally over a period of 5 to 10 hours, preferably 6 to 7 hours andafter the addition has ended, mixed into the reaction mixture in thetemperature range named above customarily for a further 5 to 10 hours,preferably 7 hours.

Surprisingly, in addition to the monomeric tetraphenylated compound,e.g. 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane, oligomers orpolymers thereof were also found in the mixture obtained after step (A).It was wholly unexpected that the quantity ratio of adamantane monomerof Formula XX to adamantane oligomer or polymer of Formula XXI ordiamantane monomer of Formula XXII to diamantane oligomer or polymer ofFormula XXIII was controllable through the quantities of adamantane ordiamantane, halogeno benzene compound (e.g. bromobenzene), and secondcatalyst component (e.g. tert.-butyl bromide) used. The molar ratio ofadamantane or diamantane to halogeno benzene compound to second catalystcomponent in the reaction mixture of step (A) is preferably1:(5-15):(2-10) and even more preferably 1:(8-12):(4-8).

In the compounds with the Formulae XX, XXI, XXII, and XXIII, theposition of the halogen substituent W is undefined. Preferably, themixtures comprise meta- and para-isomers which, unlike all para-isomers,advantageously produce improved solubility and good film properties. Inthe reaction mixture of step (A), in addition to monomers and oligomersor polymers, starting components and by-products, such as not whollyphenylated adamantanes, can also occur.

The mixture resulting from step (A) is optionally worked up usingmethods known to those skilled in the art. For example, it may benecessary to remove non-reacted halogen phenyl compound, saybromobenzene, from the mixture in order to obtain a product, usable forfurther reaction, with a high proportion of compounds of Formulae XX,XXI, XXII, and XXIII. Any solvent or solvent mixture which is misciblewith the halogeno benzene compound, say bromobenzene, and is suitablefor the precipitation of the compounds of Formulae XX, XXI, XXII, andXXIII may be used for the isolation of such a product. It is preferredto introduce the mixture resulting from step (A) into a nonpolar solventor solvent mixture, e.g. by dropping in, with preference being given tothe use of aliphatic hydrocarbons with 7 to 20 carbon atoms or mixturesthereof and in particular at least one component selected from heptanefraction (boiling point 93-99° C.), octane fraction (boiling point98-110° C.) and alkane mixture currently commercially available fromHoneywell International Inc. under the tradename Spezial Benzin 80-110°C. (petroleum ether with boiling point of 80-110° C.). Spezial Benzin80-110° C. (petroleum ether with boiling point of 80-110° C.) is mostpreferred. The weight ratio of organic mixture to nonpolar solvent ispreferably about 1:2 to about 1:20, more preferably about 1:5 to about1:13, and even more preferably about 1:7 to about 1:11. Alternatively, apolar solvent or solvent mixture (e.g. methanol or ethanol) can be usedfor the working-up of the mixture obtained after step (A), but it isless preferred, as the product mixture then precipitates out as arubbery composition.

We have found that the peak ratio of monomer resulting from step (A)above to its dimer and trimer and oligomer in the reaction mixtureshifts dramatically if the step (A) mixture is precipitated into certainsolvents. This discovery advantageously allows one skilled in the art toadjust process conditions in order to achieve a targeted ratio ofmonomer to dimer and trimer and oligomer. To reduce this ratio,preferably, a solvent is used in which the monomer and oligomer orpolymer have different solubilities.

Preferred solvents for achieving this monomer to dimer and trimer ratioshift include Spezial Benzin 80-110° C. (petroleum ether with boilingpoint of 80° C.-110° C.), ligroine (boiling point 90-110° C.), andheptane (boiling point 98° C.). The more preferred solvent is SpezialBenzin. More specifically, to achieve a shift from about 3:1monomer:dimer+trimer+oligomer to about 1:1, the step (A) mixture isprecipitated into Spezial Benzin or to attain a shift from about 3:1monomer:dimer+trimer+oligomer to about 1.7-2.0:1.0, the step (A)reaction mixture is precipitated into ligroine and heptane. We know thatthese substantial changes in peak distribution at precipitation areexplained by the loss of monomer in the precipitation filtrates: 2/3loss in Spezial Benzin and ≧1/3 loss in ligroine and heptane, whichcorrespond to monomer yield losses of 50 and 25-33%. In order for theratio monomer:dimer+trimer+oligomer 3:1 to remain unchanged, the step(A) reaction mixture is precipitated into methanol where no yield lossesare observed. This is corroborated by determination of yield losses ofthe filtrates and GPC analysis of the filtrates.

Like the synthesis described by Ortiz, the Friedel-Crafts reaction whichis carried out according to a preferred version in step (A) of thepresent process starts direct from adamantane which is coupled with thehalogeno benzene compound. Compared with previous syntheses of e.g.1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane by Reichert et al., thepresent process is particularly advantageous because it is no longernecessary to produce tetrabrominated adamantanes first, which saves areaction step. Also, less unwanted benzene forms.

It is known to those skilled in the art that the halogen radical W inthe compounds of Formulae XX, XXI, XXII, and XXIII above can also beintroduced, apart from a direct reaction of adamantane with halogenphenyl compound (e.g. with the help of a Friedel-Crafts reaction), by amulti-stage synthesis, for example, by coupling adamantane with a phenylcompound (i.e. without halogen radical W) followed by introduction ofthe radical W say through addition with W₂ (e.g. Br₂) although this isnot preferred.

In step (B) of the preferred process, the (optionally worked-up) mixtureobtained after step (A) is reacted with terminal alkyne of the formulaR₁C≡CH where R₁ is as previously defined.

In the formula R₁C≡CH, R₁ is identical with the previously describedradical R₁ of the adamantane product of Formulae III and IV and thediamantane product of Formulae V and VI. Accordingly it is mostpreferred to use ethynyl benzene (phenylacetylene) as terminal alkynefor the reaction in step (B).

In order, in step (B), to couple the terminal alkyne to the halogenobenzene radicals located at the adamantane system, all conventionalcoupling methods suitable for this purpose may be used, as described forexample in Diederich, F., and Stang, P. J., (Eds.) “Metal-CatalyzedCross-Coupling Reactions”, Wiley-VCH 1998 and March, J., “AdvancedOrganic Chemistry”, 4th Edition, John Wiley & Sons 1992, pages 717/718.

When Y on the phenyl groups is attached to two cage structure bridgeheadcarbons in Formula XXI above or in Formula XXIII above, Y may react withphenylacetylene to generate terminal alkyne groups.

In a preferred version of the process according to the invention, thereaction of the (optionally worked-up) mixture obtained after step (A)with terminal alkyne is carried out in the presence of a catalyst systemas used in the so-called Sonogashira coupling (cf. Sonogashira; Tohda;Hagihara; Tetrahedron Lett. 1975, page 4467). It is even more preferredto use a catalyst system which in each case contains at least onepalladium-triarylphosphine complex with the formula [Ar₃P]₂PdX₂ (whereAr=aryl and X=halogen), a copper halide (e.g. Cul), a base (e.g. atrialkylamine), a triarylphosphine and a co-solvent. According to theinvention, this preferred catalyst system can equally well consist ofthe named components. The co-solvent preferably contains at least onecomponent selected from toluene, xylene, chlorobenzene,N,N-dimethylformamide and 1-methyl-2-pyrrolidone (N-methylpyrrolidone(NMP)). A catalyst system which contains the componentsbis-(triphenylphosphine)palladium(II)dichloride (i.e. [Ph₃P]₂₋PdCl₂),triphenylphosphine (i.e. [Ph₃P]), copper(I)-iodide, triethylamine andtoluene as co-solvent is most preferred.

The preferred procedure for the reaction of the mixture obtained fromstep (A) (and optionally worked-up) with terminal alkyne is that themixture is first mixed with the base (e.g. triethylamine) and theco-solvent (e.g. toluene) and this mixture is stirred for some minutesat room temperature. The palladium-triphenylphosphine complex (e.g.Pd(PPh₃)₂Cl₂), triphenylphosphine (PPh₃) and copper halide (e.g.copper(I)-iodide) are then added, and this mixture is heated in atemperature range of 50° C. to 90° C. (more preferably 80° C. to 85°C.). Terminal alkyne is then added in the named temperature range within1 to 20 hours (more preferably 3 hours). After the ending of theaddition, the mixture is heated for at least 5 to 20 hours (morepreferably 12 hours) at a temperature of 75° C. to 85° C. (morepreferably 80° C.). Solvent is then added to the reaction solution anddistilled off under reduced pressure. Preferably, after filtration, thereaction solution is then cooled to a temperature of 20° C. to 30° C.(more preferably 25° C.). Finally, the reaction mixture of step (B), inparticular for the removal of metal traces (e.g. Pd), is worked up withconventional methods which are known to those skilled in the art.

The peak ratio of monomer resulting from step (B) above to its dimer andtrimer and oligomer in the reaction mixture shifts if the step (B)mixture is precipitated into certain solvents.

Surprisingly, it transpired that the reaction sequence starting directfrom adamantane leads to an oligomeric or polymeric content in thereaction product of step (A) which can be controlled via the use ratioof adamantane, halogeno benzene compound and the second catalystcomponent, say tert.-butyl bromide. In corresponding manner, the benzenecontent in the reaction mixture of step (A) is also successfullyregulated via this use ratio, which, because of the toxicity of benzenein industrial-scale syntheses, is of great importance. The oligomeric orpolymeric content permits the same secondary chemistry as the monomer(e.g. 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane, i.e. the oligomeror polymer is just as accessible as the monomer for the reaction withthe terminal alkyne in step (B)).

Adhesion Promoter:

The phrase “adhesion promoter” as used herein means any component thatwhen added to thermosetting component, improves the adhesion thereof tosubstrates compared with thermosetting component alone.

The phrase “compound having at least bifunctionality” as used hereinmeans any compound having at least two functional groups capable ofinteracting or reacting, or forming bonds as follows. The functionalgroups may react in numerous ways including addition reactions,nucleophilic and electrophilic substitutions or eliminations, radicalreactions, etc. Further alternative reactions may also include theformation of non-covalent bonds, such as Van der Waals, electrostaticbonds, ionic bonds, and hydrogen bonds.

Adhesion promoter is disclosed in our commonly assigned pending patentapplication 60/350187 filed Jan. 15, 2002 which is incorporated hereinby reference in its entirety.

In the adhesion promoter, preferably at least one of the firstfunctionality and the second functionality is selected from Sicontaining groups; N containing groups; C bonded to O containing groups;hydroxyl groups; and C double bonded to C containing groups. Preferably,the Si containing groups are selected from Si—H, Si—O, and Si—N; the Ncontaining groups are selected from such as C—NH₂ or other secondary andtertiary amines, imines, amides, and imides; the C bonded to Ocontaining groups are selected from ═CO, carbonyl groups such as ketonesand aldehydes, esters, —COOH, alkoxyls having 1 to 5 carbon atoms,ethers, glycidyl ethers; and epoxies; the hydroxyl group is phenol; andthe C double bonded to C containing groups are selected from allyl andvinyl groups. For semiconductor applications, the more preferredfunctional groups include the Si containing groups; C bonded to Ocontaining groups; hydroxyl groups; and vinyl groups.

An example of a preferred adhesion promoter having Si containing groupsis silanes of the Formula XXIV: (R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n)wherein R₂, R₃, R₄, and R₅ each independently represents hydrogen,hydroxyl, unsaturated or saturated alkyl, substituted or unsubstitutedalkyl where the substituent is amino or epoxy, saturated or unsaturatedalkoxyl, unsaturated or saturated carboxylic acid radical, or aryl; atleast two of R₂, R₃, R₄, and R₅ represent hydrogen, hydroxyl, saturatedor unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylicacid radical; and k+l+m+n≦4. Examples include vinylsilanes such asH₂C═CHSi(CH₃)₂H and H₂C═CHSi(R₆)₃ where R₆ is CH₃O, C₂H₅O, AcO, H₂C═CH,or H₂C═C(CH₃)O—, or vinylphenylmethylsilane; allylsilanes of the formulaH₂C═CHCH₂—Si(OC₂H₅)₃ and H₂C═CHCH₂—Si(H)(OCH₃)₂ glycidoxypropylsilanessuch as (3-glycidoxypropyl)methyldiethoxysilane and(3-glycidoxypropyl)trimethoxysilane; methacryloxypropylsilanes of theformula H₂C═(CH₃)COO(CH₂)₃—Si(OR₇)₃ where R₇ is an alkyl, preferablymethyl or ethyl; aminopropylsilane derivatives includingH₂N(CH₂)₃Si(OCH₂CH₃)₃, H₂N(CH₂)₃Si(OH)₃, orH₂N(CH₂)₃OC(CH₃)₂CH═CHSi(OCH₃)₃. The aforememtioned silanes arecommercially available from Gelest.

An example of a preferred adhesion promoter having C bonded to Ocontaining groups is glycidyl ethers including but not limited to1,1,1-tris-(hydroxyphenyl)ethane tri-glycidyl ether which iscommercially available from TriQuest.

An example of a preferred adhesion promoter having C bonded to Ocontaining groups is esters of unsaturated carboxylic acids containingat least one carboxylic acid group. Examples include trifunctionalmethacrylate ester, trifunctional acrylate ester, trimethylolpropanetriacrylate, dipentaerythritol pentaacrylate, and glycidyl methacrylate.The foregoing are all commercially available from Sartomer.

An example of a preferred adhesion promoter having vinyl groups is vinylcyclic pyridine oligomers or polymers wherein the cyclic group ispyridine, aromatic, or heteroaromatic. Useful examples include but notlimited to 2-vinylpyridine and 4-vinylpyridine, commercially availablefrom Reilly; vinyl aromatics; and vinyl heteroaromatics including butnot limited to vinyl quinoline, vinyl carbazole, vinyl imidazole, andvinyl oxazole.

An example of a preferred adhesion promoter having Si containing groupsis the polycarbosilane disclosed in commonly assigned copending allowedU.S. patent application Ser. No. 09/471299 filed Dec. 23, 1999incorporated herein by reference in its entirety. The polycarbosilane isof the Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted orunsubsalltituted alkylene, cycloalkylene, vinylene, allylene, orarylene; R₉, R₁₀, R₁₁, R₁₀, R₁₅, and R₁₆ each independently representshydrogen atom or organo group comprising alkyl, alkylene, vinyl,cycloalkyl, allyl, or aryl and may be linear or branched; R₁₃ representsorganosilicon, silanyl, siloxyl, or organo group; and p, q, r, and ssatisfy the conditions of [4≦p+q+r+s≦100,000], and q and r and s maycollectively or independently be zero. The organo groups may contain upto 18 carbon atoms but generally contain from about 1 to about 10 carbonatoms. Useful alkyl groups include —CH₂— and —(CH₂)_(t)— where t>1.

Preferred polycarbosilanes of the present invention include dihydridopolycarbosilanes in which R₈ is a substituted or unsubstituted alkyleneor phenyl, R₉ group is a hydrogen atom and there are no appendentradicals in the polycarbosilane chain; that is, q, r, and s are allzero. Another preferred group of polycarbosilanes are those in which theR₉, R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆ groups of Formula XXV are substituted orunsubstituted alkenyl groups having from 2 to 10 carbon atoms. Thealkenyl group may be ethenyl, propenyl, allyl, butenyl or any otherunsaturated organic backbone radical having up to 10 carbon atoms. Thealkenyl group may be dienyl in nature and includes unsaturated alkenylradicals appended or substituted on an otherwise alkyl or unsaturatedorganic polymer backbone. Examples of these preferred polycarbosilanesinclude dihydrido or alkenyl substituted polycarbosilanes such aspolydihydridocarbosilane, polyallylhydrididocarbosilane and randomcopolymers of polydihydridocarbosilane and polyallylhydridocarbosilane.

In the more preferred polycarbosilanes, the R₉ group of Formula XXV is ahydrogen atom and R₈ is methylene and the appendent radicals q, r, and sare zero. Other preferred polycarbosilane compounds of the invention arepolycarbosilanes of Formula XXV in which R₉ and R₁₅ are hydrogen, R₈ andR₁₇ are methylene, and R₁₆ is an alkenyl, and appendent radicals q and rare zero. The polycarbosilanes may be prepared from well known prior artprocesses or provided by manufacturers of polycarbosilane compositions.In the most preferred polycarbosilanes, the R₉ group of Formula XXV is ahydrogen atom; R₈ is —CH₂—; q, r, and s are zero and p is from 5 to 25.These most preferred polycarbosilanes may be obtained from StarfireSystems, Inc. Specific examples of these most preferred polycarbosilanesfollow: Peak Weight Average Molecular Molecular Weight WeightPolycarbosilane (Mw) Polydispersity (Mp) 1   400-1,400   2-2.5 330-500 2330 1.14 320 3 10,000-14,000 10.4-16   1160 (with 10% allyl groups) 42,400 3.7 410 (with 75% allyl groups)

As can be observed in Formula XXV, the polycarbosilanes utilized in thesubject invention may contain oxidized radicals in the form of siloxylgroups when r>0. Accordingly, R₁₃ represents organosilicon, silanyl,siloxyl, or organo group when r>0. It is to be appreciated that theoxidized versions of the polycarbosilanes (r>0) operate very effectivelyin, and are well within the purview of the present invention. As isequally apparent, r can be zero independently of p, q, and s the onlyconditions being that the radicals p, q, r, and s of the Formula XXVpolycarbosilanes must satisfy the conditions of [4<p+q+r+s<100,000], andq and r can collectively or independently be zero.

The polycarbosilane may be produced from starting materials that arepresently commercially available from many manufacturers and by usingconventional polymerization processes. As an example of synthesis of thepolycarbosilanes, the starting materials may be produced from commonorgano silane compounds or from polysilane as a starting material byheating an admixture of polysilane with polyborosiloxane in an inertatmosphere to thereby produce the corresponding polymer or by heating anadmixture of polysilane with a low molecular weight carbosilane in aninert atmosphere to thereby produce the corresponding polymer or byheating an admixture of polysilane with a low molecular carbosilane inan inert atmosphere and in the presence of a catalyst such aspolyborodiphenylsiloxane to thereby produce the corresponding polymer.Polycarbosilanes may also be synthesized by Grignard Reaction reportedin U.S. Pat. No. 5,153,295 hereby incorporated by reference.

An example of a preferred adhesion promoter having hydroxyl groups isphenol-formaldehyde resins or oligomers of the Formula XXVI:—[R₁₈C₆H₂(OH)(R₁₉)]_(u)— where R₁₈ is substituted or unsubstitutedalkylene, cycloalkylene, vinyl, allyl, or aryl; R₁₉ is alkyl, alkylene,vinylene, cycloalkylene, allylene, or aryl; and u=3-100. Examples ofuseful alkyl groups include —CH₂— and —(CH₂)_(v)— where v>1. Aparticularly useful phenol-formaldehyde resin oligomer has a molecularweight of 1500 and is commercially available from SchenectadyInternational Inc.

The present adhesion promoter is preferably added in small, effectiveamounts from about 0.5% to up to 20% based on the weight of the presentthermosetting composition and amounts up to about 5.0% by weight of thecomposition are generally more preferred.

By combining the adhesion promoter with the thermosetting component andsubjecting the composition to thermal or a high energy source, theresulting compositions have superior adhesion characteristics throughoutthe entire polymer so as to ensure affinity to any contacted surface ofthe coating. The present adhesion promoters also improve striationcontrol, viscosity, and film uniformity. Visual inspection confirms thepresence of improved striation control.

The present compositions may also comprise additional components such asadditional adhesion promoters, antifoam agents, detergents, flameretardants, pigments, plasticizers, stabilizers, and surfactants.

Porogen:

The term “pore” as used herein includes void and cells in a material andany other term meaning space occupied by gas in the material.Appropriate gases include relatively pure gases and mixtures thereof.Air, which is predominantly a mixture of N₂ and O₂, is commonlydistributed in the pores but pure gases such as nitrogen, helium, argon,CO₂, or CO are also contemplated. Pores are typically spherical but mayalternatively or additionally include tubular, lamellar, discoidal,voids having other shapes, or a combination of the preceding shapes andmay be open or closed. The term “porogen” as used herein means adecomposable material that is radiation, thermally, chemically, ormoisture decomposable, degradable, depolymerizable, or otherwise capableof breaking down and includes solid, liquid, or gaseous material. Thedecomposed porogen is removable from or can volatilize or diffusethrough a partially or fully cross-linked matrix to create pores in asubsequently fully cured matrix and thus, lower the matrix's dielectricconstant and includes sacrificial polymers. Supercritical materials suchas CO₂ may be used to remove porogen and decomposed porogen fragments.Preferably, for a thermally decomposable porogen, the porogen comprisesa material having a decomposition temperature less than the glasstransition temperature (Tg) of a material combined with it and greaterthan the curing temperature of the material combined with it.Preferably, the present porogens have a degradation or decompositiontemperature of about 350° C. or greater. Preferably, the degraded ordecomposed porogens volatilize at a temperature greater than the curetemperature of the material with which the porogen is combined and lessthan the Tg of the material. Preferably, the degraded or decomposedporogens volatilize at a temperature of about 96° C. or greater.

The phrase “porogen bonds to the thermosetting component” coversaddition reactions, nucleophilic and electrophilic substitutions oreliminations, radical reactions, etc. Further alternative reactions mayalso include the formation of non-covalent bonds, such as Van der Waals,electrostatic bonds, ionic bonds, and hydrogen bonds.

Although International Patent Publication WO 00/31183 teaches that aporogen may be added to thermosettable benzocyclobutene, polyarylene, orthermosettable perfluoroethylene monomer to increase porosity thereofand thus, lower the dielectric constant of that resin, the referenceteaches that a porogen that is known to function well with a firstmatrix system will not necessarily function well with another matrixsystem.

The present porogens preferably comprise unsubstituted polynorbornene,substituted polynorbornene, polycaprolactone, unsubstituted polystyrene,substituted polystyrene, polyacenaphthylene homopolymer, andpolyacenaphthylene copolymer. The more preferred porogen is substitutedpolynorbornene. Preferably, the porogen has functional groups selectedfrom the group consisting of epoxy, hydroxy, carboxylic acid groups,amino, and ethynyl. Preferably, the porogen has a functional group on atleast one of its ends.

Preferably, the porogen is bonded to the thermosetting component throughan ethynyl containing group. In one embodiment, the ethynyl containinggroup is first reacted with the porogen as shown in FIGS. 5, 7, 9, and11. In a preferred embodiment, the ethynyl containing group is firstreacted with the thermosetting component as shown in FIGS. 4, 6, 8, and10. In FIGS. 4 though 11, although only1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene isshown, it is understood that similar reaction occur for other usefulthermosetting components including1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane and1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis{3″″,4″″-bromophenyl)adamantane.Useful ethynyl containing groups include fluorine; amine; or hydroxy;and preferably, are acetylene; 4-ethynylaniline;3-hydroxyphenylacetylene; 4-fluorophenylacetylene; and1-ethylcyclohexylamine. Preferably, a covalent bond forms between theporogen and the thermosetting component through the ethynyl containinggroup.

Useful polyacenaphthylene homopolymers may have weight average molecularweights ranging from preferably about 300 to about 20,000; morepreferably about 300 to about 10,000; and most preferably about 300 toabout 7,000.

The amount of thermosetting component used is about 50 to about 90weight percent while the amount of porogen used is about 10 to about 50weight percent. Preferably, an adhesion promoter as described above isadded to the porogen bonded to the thermosetting component. Based on acomposition comprising the adhesion promoter and the porogen bonded tothe thermosetting component, about 0.1 to about 15 weight percent ofadhesion promoter is used and about 5 to about 50 weight percent porogenbonded to the thermosetting component is used.

Pore Generation:

The term “degrade” as used herein refers to the breaking of covalentbonds. Such breaking of bonds may occur in numerous ways includingheterolytic and homolytic breakage. The breaking of bonds need not becomplete, i.e., not all breakable bonds must be cleaved. Furthermore,the breaking of bonds may occur in some bonds faster than in others.Ester bonds, for example, are generally less stable than amide bonds,and therefore, are cleaved at a faster rate. Breakage of bonds may alsoresult in the release of fragments differing from one another, dependingon the chemical composition of the degraded portion.

In the pore generation process, for thermally degradable porogens,thermal energy is applied to the porogen bonded to the thermosettingcomponent to substantially degrade or decompose the porogen into itsstarting components or monomers. As used herein, “substantially degrade”preferably means at least 80 weight percent of the porogen degrades ordecomposes. For the preferred thermosetting components of Formulae I andII above, the Tg is from about 400° C. to about 450° C. so the presentporogens which have a degradation or decomposition temperature of about350° C. or greater are particularly useful with this thermosettingcomponent.

Thermal energy is also applied to volatilize the substantially degradedor decomposed porogen out of the thermosetting component matrix.Preferably, the same thermal energy is used for both the degradation andvolatilization steps. As the amount of volatilized degraded porogenincreases, the resulting porosity of the thermosetting componentincreases. For the preferred thermosetting components of Formulae I andII above, the Tg is from about 400° C. to about 450° C. so the presentsubstantially degraded porogens which have a volatilization temperatureof about 96° C. or greater are particularly useful with saidthermosetting component.

Preferably, the cure temperature used for cross-linking thethermosetting component will also substantially degrade the porogen andvolatilize it out of the thermosetting matrix. Typical cure temperatureand conditions will be described in the Utility section below.

The resulting pores may be uniformly or randomly dispersed throughoutthe matrix. Preferably, the pores are uniformly dispersed throughout thematrix.

Alternatively, other procedures or conditions which at least partiallyremove the porogen without adversely affecting the thermosettingcomponent may be used. Preferably, the porogen is substantially removed.Typical removal methods include, but are not limited to, exposure toradiation, such as but not limited to, electromagnetic radiation such asultraviolet, x-ray, laser, or infrared radiation; mechanical energy suchas sonication or physical pressure; or particle radiation such as gammaray, alpha particles, neutron beam, or electron beam.

Utility:

The term “layer” as used herein includes film and coating.

The term “low dielectric constant polymer” as used herein refers to anorganic, organometallic, or inorganic polymer with a dielectric constantof approximately 3.0, or lower. The low dielectric material is typicallymanufactured in the form of a thin layer having a thickness from 100 to25,000 Angstroms but also may be used as thick films, blocks, cylinders,spheres etc.

The present composition of thermosetting component, adhesion promoter,and porogen is useful in lowering the dielectric constant of a material.Preferably, the dielectric material has a dielectric constant k of lessthan or equal to about 3.0 and more preferably, from about 1.9 to 3.0.The dielectric material has a glass transition temperature of preferablyat least about 350° C.

Layers of the instant compositions of thermosetting component, adhesionpromoter, and porogen may be formed by solution techniques such asspraying, rolling, dipping, spin coating, flow coating, or casting, withspin coating being preferred for microelectronics. Preferably, thepresent composition is dissolved in a solvent. Suitable solvents for usein such solutions of the present compositions include any suitable pureor mixture of organic, organometallic, or inorganic molecules that arevolatized at a desired temperature. Suitable solvents include aproticsolvents, for example, cyclic ketones such as cyclopentanone,cyclohexanone, cycloheptanone, and cyclooctanone; cyclic amides such asN-alkylpyrrolidinone wherein the alkyl has from about 1 to 4 carbonatoms; and N-cyclohexylpyrrolidinone and mixtures thereof. A widevariety of other organic solvents may be used herein insofar as they areable to aid dissolution of the adhesion promoter and at the same timeeffectively control the viscosity of the resulting solution as a coatingsolution. Various facilitating measures such as stirring and/or heatingmay be used to aid in the dissolution. Other suitable solvents includemethyethylketone, methylisobutylketone, dibutyl ether, cyclicdimethylpolysiloxanes, butyrolactone, γ-butyrolactone, 2-heptanone,ethyl 3-ethoxypropionate, polyethylene glycol [dilmethyl ether,propylene glycol methyl ether acetate (PGMEA), and anisole, andhydrocarbon solvents such as mesitylene, xylenes, benzene, and toluene.Preferred solvent is cyclohexanone. Typically, layer thicknesses arebetween 0.1 to about 15 microns. As a dielectric interlayer formicroelectronics, the layer thickness is generally less than 2 microns.

The present composition may be used in electrical devices and morespecifically, as an interlayer dielectric in an interconnect associatedwith a single integrated circuit (“IC”) chip. An integrated circuit chiptypically has on its surface a plurality of layers of the presentcomposition and multiple layers of metal conductors. It may also includeregions of the present composition between discrete metal conductors orregions of conductor in the same layer or level of an integratedcircuit.

In application of the instant polymers to ICs, a solution of the presentcomposition is applied to a semiconductor wafer using conventional wetcoating processes such as, for example, spin coating; other well knowncoating techniques such as spray coating, flow coating, or dip coatingmay be employed in specific cases. As an illustration, a cyclohexanonesolution of the present composition is spin-coated onto a substratehaving electrically conductive components fabricated therein and thecoated substrate is then subjected to thermal processing. An exemplaryformulation of the instant composition is prepared by dissolving thepresent composition in cyclohexanone solvent under ambient conditionswith strict adherence to a clean-handling protocol to prevent tracemetal contamination in any conventional apparatus having a non-metalliclining. The resulting solution comprises based on the total solutionweight, from preferably about 2 to about 30 weight percent ofthermosetting component, adhesion promoter, and porogen, and about 70 toabout 98 weight percent solvent and more preferably about 5 to about 25weight percent of thermosetting component, adhesion promoter, andporogen, and about 75 to about 95 weight percent solvent.

An illustration of the use of the present invention follows. Applicationof the instant compositions to form a layer onto planar or topographicalsurfaces or substrates may be carried out by using any conventionalapparatus, preferably a spin coater, because the compositions usedherein have a controlled viscosity suitable for such a coater.Evaporation of the solvent by any suitable means, such as simple airdrying during spin coating, by exposure to an ambient environment, or byheating on a hot plate up to 350° C., may be employed. The substrate mayhave on it at least one layer of the present preferred composition ofthermosetting component, adhesion promoter, and porogen.

Substrates contemplated herein may comprise any desirable substantiallysolid material. Particularly desirable substrate layers comprise films,glass, ceramic, plastic, metal or coated metal, or composite material.In preferred embodiments, the substrate comprises a silicon or galliumarsenide die or wafer surface, a packaging surface such as found in acopper, silver, nickel or gold plated leadframe, a copper surface suchas found in a circuit board or package interconnect trace, a via-wall orstiffener interface (“copper” includes considerations of bare copper andits oxides), a polymer-based packaging or board interface such as foundin a polyimide-based flex package, lead or other metal alloy solder ballsurface, glass and polymers. Useful substrates include silicon, siliconnitride, silicon oxide, silicon oxycarbide, silicon dioxide, siliconcarbide, silicon oxynitride, titanium nitride, tantalum nitride,tungsten nitride, aluminum, copper, tantalum, organosiloxanes, organosilicon glass, and fluorinated silicon glass. In other embodiments, thesubstrate comprises a material common in the packaging and circuit boardindustries such as silicon, copper, glass, and polymers. The presentcompositions may also be used as a dielectric substrate material inmicrochips, multichip modules, laminated circuit boards, or printedwiring boards. The circuit board made up of the present composition willhave mounted on its surface patterns for various electrical conductorcircuits. The circuit board may include various reinforcements, such aswoven non-conducting fibers or glass cloth. Such circuit boards may besingle sided, as well as double sided.

Layers made from the present compositions possess a low dielectricconstant, high thermal stability, high mechanical strength, andexcellent adhesion to electronic substrate surfaces. Because theadhesion promoter is molecularly dispersed, these layers demonstrateexcellent adhesion to all affixed surfaces including underlyingsubstrates and overlaid capping or masking layers, such as SiO₂ andSi₃N₄ capping layers. The use of these layers eliminates the need for anadditional process step in the form of at least one primer coatingapplication to achieve adhesion of the film to a substrate and/oroverlaid surface.

After application of the present composition to an electronictopographical substrate, the coated structure is subjected to a bake andcure thermal process at increasing temperatures ranging from about 50°C. up to about 450° C. to polymerize the coating. The curing temperatureis at least about 300° C. because a lower temperature is insufficient tocomplete the reaction herein. Generally, it is preferred that curing iscarried out at temperatures of from about 375° C. to about 425° C.Curing may be carried out in a conventional curing chamber such as anelectric furnace, hot plate, and the like and is generally performed inan inert (non-oxidizing) atmosphere (nitrogen) in the curing chamber. Inaddition to furnace or hot plate curing, the present compositions mayalso be cured by exposure to ultraviolet radiation, microwave radiation,or electron beam radiation as taught by commonly assigned patentpublication PCT/US96/08678 and U.S. Pat. Nos. 6,042,994; 6,080,526;6,177,143; and 6,235,353, which are incorporated herein by reference intheir entireties. Any non oxidizing or reducing atmospheres (e.g.,argon, helium, hydrogen, and nitrogen processing gases) may be used inthe practice of the present invention, if they are effective to conductcuring of the present adhesion promoter-modified thermosetting componentto achieve the low k dielectric layer herein.

While not to be construed as limiting, it is observed that theprocessing used to prepare the present low dielectric constantcomposition results in a homogeneous solution of thermosettingcomponent, adhesion promoter, and porogen. The preferred silane adhesionpromoter advantageously serves multiple functions in the low dielectricconstant composition. For example, the processing of the presentcomposition enables the preferred polycarbosilane adhesion promoter tointeract with both the porogen and the unsaturated structures ofthermosetting component. It is believed that the silane portions of thepreferred polycarbosilane interact with the porogen and thermosettingcomponent. It is speculated that the polycarbosilane acts as asurfactant or emulsification agent to uniformly disperse the porogenwithin the thermosetting component in the low dielectric composition.This is critical to producing a composition that gives a homogeneousfilm (or layer) with uniformly dispersed pores of very small dimension.The silane portion of the polycarbosilane also reacts with the substratesurfaces, thereby creating a chemically bonded adherent interface forthe dominant thermosetting monomer precursor. It has been proposed thatsilylene/silyl radicals being available throughout the composition actas attachment sources to fasten and secure any interface surface ofcontact by chemical bonding therewith. The interactions between thevarious components and the reactions of the silane portion may occurduring formulation and treatment prior to layer formation. As indicated,the dispersion of silane functionality with the porogen andthermosetting component throughout the composition accounts for theuniform porosity in the resulting layers. The dispersion of the silanefunctionality also leads to reactive radicals as well as the superbadhesion of the instant layers to both underlying substrate surfaces aswell as overlayered surface structures such as cap or masking layers.Crucial to the materials discovered herein are the findings that thepreferred Formula XXV polycarbosilane adhesion promoters have a hydridosubstituted silicon in the backbone structure of the polycarbosilane.This feature of the polycarbosilane enables it to: (1) mix uniformlywith the porogen to form a homogeneous composition, (2) be reactive withthermosetting component; (3) uniformly blend and disperse the porogenwithin the thermosetting component providing a uniform compositionleading to uniform distribution of small pores in the final porouslayer, and (4) generate a polycarbosilane-modified thermosettingcomposition and porous layer that possesses improved adhesionperformance.

As indicated earlier, the present adhesion promoter-modifiedthermosetting component (a) coating may act as an interlayer and becovered by other coatings, such as other dielectric (SiO₂) coatings,SiO₂ modified ceramic oxide layers, silicon containing coatings, siliconcarbon containing coatings, silicon nitrogen containing coatings,silicon-nitrogen-carbon containing coatings, diamond like carboncoatings, titanium nitride coatings, tantalum nitride coatings, tungstennitride coatings, aluminum coatings, copper coatings, tantalum coatings,organosiloxane coatings, organo silicon glass coatings, and fluorinatedsilicon glass coatings. Such multilayer coatings are taught in U.S. Pat.No. 4,973,526, which is incorporated herein by reference. And, as amplydemonstrated, the present polycarbosilane-modified thermosettingcomponent (a) prepared in the instant process may be readily formed asinterlined dielectric layers between adjacent conductor paths onfabricated electronic or semiconductor substrates.

The present films may be used in dual damascene (such as copper)processing and substractive metal (such as aluminum oraluminum/tungsten) processing for integrated circuit manufacturing. Thepresent compositions may be used as an etch stop, hardmask, air bridge,or passive coating for enveloping a completed wafer. The presentcomposition may be used in a desirable all spin-on stacked film astaught by Michael E. Thomas, “Spin-On Stacked Films for Low k_(eff)Dielectrics”, Solid State Technology (July 2001), incorporated herein inits entirety by reference. The present layers may be used in stacks withother layers comprising organosiloxanes such as taught by commonlyassigned U.S. Pat. No. 6,143,855 and pending U.S. Ser. No. 10/078919filed Feb. 19, 2002; Honeywell International Inc.'s commerciallyavailable HOSP® product; nanoporous silica such as taught by commonlyassigned U.S. Pat. No. 6,372,666; Honeywell International Inc.'scommercially available NANOGLASS® E product; organosilsesquioxanestaught by commonly assigned WO 01/29052; and fluorosilsesquioxanestaught by commonly assigned WO 01/29141, incorporated herein in theirentirety.

Analytical Test Methods:

Proton NMR: A 2-5 mg sample of the material to be analyzed was put intoan NMR tube. About 0.7 ml deuterated chloroform was added. The mixturewas shaken by hand to dissolve the material. The sample was thenanalyzed using a Varian 400 MHz NMR.

High Performance Liquid Chromatography (HPLC): A HPLC with a Phenomenexluna Phenyl-Hexyl 250×4.6 mm 5 micron column was used. The columntemperature was set at 40° C. Water and acetonitrile were used toimprove peak separation. TIME WATER ACETONITRILE Initial 20%  80% 10minutes  0% 100% 30 minutes  0% 100%

The following experimental conditions were used: INJECTION VOLUME 10microliters DETECTION UV at 200 nm STOP TIME 30 minutes POST TIME 5minutes

The samples were prepared as follows.

For a mixture of the halogenated intermediate such as the mixture of1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane and1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl]adamant-7′-yl]benzene ofPreparation 1 below, the reaction mixture (0.5-1 milliliter) was shakenwith approximately 4% HCl (several milliliters). The organic layer wasshaken with water. An organic layer sample (twenty microliters) wastaken and added to acetonitrile (one milliliter).

For a mixture of the final product such as the mixture of1,3,5,7-tetrakis[3′/4′-(phenylethynyl)phenyl]adamantane and1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzeneof Preparation 1 below, the reaction mixture (0.5 gram) was mixed withchloroform (five milliliters) and 3-5% HCl (5 milliliters) and shaken.The organic layer was washed by water. An organic layer sample (100microliters) was added to tetrahydrofuran (0.9 milliliter).

Gel Permeation Chromatography (GPC 1): The GPC analysis was done withWaters liquid chromatography system composed from Water 717 plusAutosampler, Waters in-line degasser, Waters 515 HPLC pump, Waters 410Differential Refractometer (RI detector), and two columns: HP PI gel 5 μMIXED D. The analysis conditions were: Mobile Phase Tetrahydrofuran(THF) Column flow (milliliters/min)  1.0 Column temperature (° C.) 40.0Detection Refractive Index, Polarity positive Analysis run time 25 minInjection quantity (μL) 50The solid product sample (10 milligrams) was prepared by dissolving intetrahydrofuran (one milliliter).

Gel Permeation Chromatography (GPC 2): This method may be used toprovide additional detail about the dimer and trimer peaks. Thefollowing conditions are used: Analysis Apparatus Shimadzu LC10Separation Column Plgel 5 μpre-column Plgel 5 μ1000 Å, 300 × 7.5 nmPlgel 5 μ500 Å, 300 × 7.5 nm Plgel 5 μ100 Å, 300 × 7.5 nm Mobile PhaseEluent A: toluene Column Flow (milliliters/minute)  1.0 ColumnTemperature (° C.) 40 Detection Refractive Index, Polarity PositiveAnalysis Run Time (minutes) 32 Trial Solution 10 milligrams/millilitertoluene Injection Quantity (μ) 50To calculate the contents, in other words area-%, the peak areabelonging to the monomer or the peak area belonging to the oligomer orpolymer is related to the total of all the peak areas in thechromatogram.

Gel Permeation Chromatography (GPC 3): Separation was performed with aWaters 2690 separation module with Waters 996 diode array and Waters 410differential refractometer detectors. The separation was performed ontwo PLgel 3 μm Mixed-E 300×7.5 mm columns with chloroform flowing at 1ml/min. Injection volumes of 25 μl of solutions of about 1 mg/mlconcentration were run in duplicate. Good reproducibility was observed.

The column was calibrated with relatively monodisperse polystyrenestandards between 20,000 and 500 molecular weight. With the lowermolecular weight standards nine distinct components could be resolvedcorresponding to butyl terminated styrene monomer through oligomers withnine styrenes. The logs of the peak molecular weight of the standardswere fit with a third order polynomial of the elution time. Theinstrumental broadening was evaluated from the ratio of the full widthat half maximum to the mean elution time of toluene.

The absorbance for Preparations 1 and 2 below was a maximum at about 284nm. The chromatograms had similar shapes at absorbance at wavelengthsbelow about 300 nm. The results presented here correspond to 254 nmabsorbance. The peaks were identified by the molecular weight of thepolystyrene that would be eluting at the same time. These values shouldnot be considered as measurements of molecular weight of the Preparation1 and 2 oligomers. The sequential elution of higher oligomers, trimers,dimers, oligomers, and incomplete oligomers at increasing times can bequantitated.

Each component was broader than that which would be observed for amonodisperse species. This width was analyzed from the full width inminutes at half maximum of the peak. To roughly account for theinstrumental broadening, we calculatedwidth_(corrected)=[width_(observed) ²−width_(instrument) ²]^(1/2)where width_(instrument) is the observed width of toluene corrected bythe ratio of the elution times of the peak to that for toluene. The peakwidth was converted to a molecular weight width through the calibrationcurve and ratioed to the peak molecular width. Since the molecularweight of styrene oligomers was proportional to the square of theirsize, the relative molecular weight width can be converted to a relativeoligomer size width by dividing by 2. This procedure accounted for thedifference in molecular configuration of the two species.

Liquid Chromatography-Mass Spectroscopy (LC-MS): This analysis wasperformed on a Finnigan/MAT TSQ7000 triple stage quadrupole massspectrometer system, with an Atmospheric Pressure Ionization (API)interface unit, using a Hewlett-Packard Series 1050 HPLC system as thechromatographic inlet. Both mass spectral ion current and variablesingle wavelength UV data were acquired for time-intensitychromatograms.

Chromatography was conducted on a Phenomenex Luna 5-micron pheny-hexylcolumn (250×4.6 mm). Sample auto-injections were generally between 5 and20 microliters of concentrated solutions, both in tetrahydrofuran andwithout tetrahydrofuran. The preferred preparation of concentratedsample solutions for analysis was dissolution in tetrahydrofuran, ofabout 5 milligrams solid product per milliliter, for 10 microliterinjections. The mobile phase flow through the column was 1.0milliliter/minute of acetonitrile/water, initially 70/30 for 1 minutethen gradient programmed to 100% acetonitrile at 10 minutes and helduntil 40 minutes.

Atmospheric Pressure Chemical Ionization (APCI) mass spectra wererecorded in both positive and negative ionization, in separateexperiments. Positive APCI was more informative of molecular structurefor these final products, providing protonated pseudomolecular ionsincluding adducts with acetonitrile matrix. The APCI corona dischargewas 5 microamps, about 5 kV for positive ionization, and about 4 kV fornegative ionization. The heated capillary line was maintained at 200° C.and the vaporizer cell at 400° C. The ion detection system afterquadrupole mass analysis was set at 15 kV conversion dynode and 1500Velectron multiplier voltage. Mass spectra were typically recorded at 1.0second/scan from about m/z 50 to 2000 a.m.u. for negative ionization,and from about m/z 150 a.m.u. up for positive ionization. In separatepositive ion experiments, the mass range was scanned up both to 2000a.m.u. in low mass tune/calibration mode and to 4000 a.m.u. in high masstune/calibration mode.

Differential Scanning Calorimetry (DSC): DSC measurements were performedusing a TA Instruments 2920 Differential Scanning Calorimeter inconjunction with a controller and associated software. A standard DSCcell with temperature ranges from 250° C. to 725° C. (inert atmosphere:50 ml/min of nitrogen) was used for the analysis. Liquid nitrogen wasused as a cooling gas source. A small amount of sample (10-12 mg) wascarefully weighed into an Auto DSC aluminum sample pan (Part #990999-901) using a Mettler Toledo Analytical balance with an accuracyof ±0.0001 grams. Sample was encapsulated by covering the pan with thelid that was previously punctured in the center to allow for outgasing.Sample was heated under nitrogen from 0° C. to 450° C. at a rate of 100°C./minute (cycle 1), then cooled to 0° C. at a rate of 100° C./minute. Asecond cycle was run immediately from 0° C. to 450° C. at a rate of 100°C./minute (repeat of cycle 1). The cross-linking temperature wasdetermined from the first cycle.

FTIR analysis: FTIR spectra were taken using a Nicolet Magna 550 FTIRspectrometer in transmission mode. Substrate background spectra weretaken on uncoated substrates. Film spectra were taken using thesubstrate as background. Film spectra were then analyzed for change inpeak location and intensity.

Dielectric Constant: The dielectric constant was determined by coating athin film of aluminum on the cured layer and then doing acapacitance-voltage measurement at 1 MHz and calculating the k valuebased on the layer thickness.

Glass Transition Temperature (Tg): The glass transition temperature of athin film was determined by measuring the thin film stress as a functionof temperature. The thin film stress measurement was performed on a KLA3220 Flexus. Before the film measurement, the uncoated wafer wasannealed at 500° C. for 60 minutes to avoid any errors due to stressrelaxation in the wafer itself. The wafer was then deposited with thematerial to be tested and processed through all required process steps.The wafer was then placed in the stress gauge, which measured the waferbow as function of temperature. The instrument calculated the stressversus temperature graph, provided that the wafer thickness and the filmthickness were known. The result was displayed in graphic form. Todetermine the Tg value, a horizontal tangent line was drawn (a slopevalue of zero on the stress vs. temperature graph). Tg value was wherethe graph and the horizontal tangent line intersect.

It should be reported if the Tg was determined after the firsttemperature cycle or a subsequent cycle where the maximum temperaturewas used because the measurement process itself may influence Tg.

Isothermal Gravimetric Analysis (ITGA) Weight Loss: Total weight losswas determined on the TA Instruments 2950 Thermogravimetric Analyzer(TGA) used in conjunction with a TA Instruments thermal analysiscontroller and associated software. A Platinel II Thermocouple and aStandard Furnace with a temperature range of 25° C. to 1000° C. andheating rate of 0.1° C. to 100° C./min were used. A small amount ofsample (7 to 12 mg) was weighed on the TGA's balance (resolution: 0.1 g;accuracy: to ±0.1%)and heated on a platinum pan. Samples were heatedunder nitrogen with a purge rate of 100 ml/min (60 ml/min going to thefurnace and 40 ml/min to the balance). Sample was equilibrated undernitrogen at 20° C. for 20 minutes, then temperature was raised to 200°C. at a rate of 10° C./minute and held at 200° C. for 10 minutes.Temperature was then ramped to 425° C. at a rate of 10° C./minute andheld at 425° C. for 4 hours. The weight loss at 425° C. for the 4 hourperiod was calculated.

Shrinkage: Film shrinkage was measured by determining the film thicknessbefore and after the process. Shrinkage was expressed in percent of theoriginal film thickness. Shrinkage was positive if the film thicknessdecreased. The actual thickness measurements were performed opticallyusing a J. A. Woollam M-88 spectroscopic ellipsometer. A Cauchy modelwas used to calculate the best fit for Psi and Delta (details onEllipsometry can be found in e.g. “Spectroscopic Ellipsometry andReflectometry” by H. G. Thompkins and William A. McGahan, John Wiley andSons, Inc., 1999).

Refractive Index: The refractive index measurements were performedtogether with the thickness measurements using a J. A. Woollam M-88spectroscopic ellipsometer. A Cauchy model was used to calculate thebest fit for Psi and Delta. Unless noted otherwise, the refractive indexwas reported at a wavelenth of 633 nm (details on Ellipsometry can befound in e.g. “Spectroscopic Ellipsometry and Reflectometry” by H. G.Thompkins and William A. McGahan, John Wiley and Sons, Inc., 1999).

Modulus and Hardness: Modulus and hardness were measured usinginstrumented indentation testing. The measurements were performed usinga MTS Nanoindenter XP (MTS Systems Corp., Oak Ridge, Tenn.).Specifically, the continuous stiffness measurement method was used,which enabled the accurate and continuous determination of modulus andhardness rather than measurement of a discrete value from the unloadingcurves. The system was calibrated using fused silica with a nominalmodulus of 72+−3.5 GPa. The modulus for fused silica was obtained fromaverage value between 500 to 1000 nm indentation depth. For the thinfilms, the modulus and hardness values were obtained from the minimum ofthe modulus versus depth curve, which is typically between 5 to 15% ofthe film thickness.

Tape Test: The tape test was performed following the guidelines given inASTM D3359-95. A grid was scribed into the dielectric layer according tothe following. A tape test was performed across the grid marking in thefollowing manner: (1) a piece of adhesive tape, preferably Scotch brand#3 m600-1/2×1296, was placed on the present layer, and pressed downfirmly to make good contact; and (2) the tape was then pulled offrapidly and evenly at an angle of 180° to the layer surface. The samplewas considered to pass if the layer remained intact on the wafer, or tohave failed if part or all of the film pulled up with the tape.

Stud Pull Test: Epoxy-coated studs were attached to the surface of awafer containing the layers of the present invention. A ceramic backingplate was applied to the back side of the wafer to prevent substratebending and undue stress concentration at the edges of the stud. Thestuds were then pulled in a direction normal to the wafer surface by atesting apparatus employing standard pull protocol steps. The stressapplied at the point of failure and the interface location were thenrecorded.

Compatibility with Solvents: Compatibility with solvents was determinedby measuring film thickness, refractive index, FTIR spectra, anddielectric constant before and after solvent treatment. For a compatiblesolvent, no significant change should be observed.

Average Pore Size Diameter: The N₂ isotherms of porous samples wasmeasured on a Micromeretics ASAP 2000 automatic isothermal N₂ sorptioninstrument using UHP (ultra high purity industrial gas) N₂, with thesample immersed in a sample tube in a liquid N₂ bath at 77° K.

For sample preparation, the material was first deposited on siliconwafers using standard processing conditions. For each sample, threewafers were prepared with a film thickness of approximately 6000Angstroms. The films were then removed from the wafers by scraping witha razor blade to generate powder samples. These powder samples werepre-dried at 180° C. in an oven before weighing them, carefully pouringthe powder into a 10 mm inner diameter sample tube, then degassing at180° C. at 0.01 Torr for >3 hours.

The adsorption and desorption N₂ sorption was then measuredautomatically using a 5 second equilibration interval, unless analysisshowed that a longer time was required. The time required to measure theisotherm was proportional to the mass of the sample, the pore volume ofthe sample, the number of data points measured, the equilibrationinterval, and the P/Po tolerance. (P is actual pressure of the sample inthe sample tube. Po is the ambient pressure outside the instrument.) Theinstrument measures the N₂ isotherm and plots N₂ versus P/Po.

The apparent BET (Brunauer, Emmett, Teller method for multi-layer gasabsorption on a solid surface disclosed in S. Brunauer, P. H. Emmett, E.Teller; J. Am. Chem. Soc., 60, 309-319 (1938)) surface area wascalculated from the lower P/Po region of the N2 adsorption isothermusing the BET theory, using the linear section of the BET equation thatgives an R² fit >0.9999.

The pore volume was calculated from the volume of N₂ adsorbed at therelative pressure P/Po value, usually P/Po ˜0.95, which is in the flatregion of the isotherm where condensation is complete, assuming that thedensity of the adsorbed N₂ is the same as liquid N₂ and that all thepores are filled with condensed N₂ at this P/Po.

The pore size distribution was calculated from the adsorption arm of theN₂ isotherm using the BJH (E. P. Barret, L. G. Joyner, P. P. Halenda; J.Am. Chem. Soc., 73, 373-380 (1951)) pore size distribution from the N2isotherm using the Kelvin equation) theory. This uses the Kelvinequation, which relates curvature to suppression of vapor pressure, andthe Halsey equation, which describes the thickness of the adsorbed N₂monolayer versus P/Po, to convert the volume of condensed N₂ versus P/Poto the pore volume in a particular range of pore sizes.

The average cylindrical pore diameter D was the diameter of a cylinderthat has the same apparent BET surface area Sa (m²/g) and pore volume Vp(cc/g) as the sample, so D(nm)=4000 Vp/Sa.

Thermal Desorption Mass Spectroscopy: Thermal Desorption MassSpectroscopy (TDMS) is used to measure the thermal stability of amaterial by analyzing the desorbing species while the material issubjected to a thermal treatment.

The TDMS measurement was performed in a high vacuum system equipped witha wafer heater and a mass spectrometer, which was located close to thefront surface of the wafer. The wafer was heated using heating lamps,which heat the wafer from the backside. The wafer temperature wasmeasured by a thermocouple, which was in contact with the front surfaceof the wafer. Heater lamps and thermocouple were connected to aprogrammable temperature controller, which allowed several temperatureramp and soak cycles. The mass spectrometer was a Hiden Analytical HALIV RC RGA 301. Both mass spectrometer and the temperature controllerwere connected to a computer, which read and recorded the massspectrometer and the temperature signal versus time.

To perform TDMS analysis, the material was first deposited as a thinfilm onto an 8 inch wafer using standard processing methods. The waferwas then placed in the TDMS vacuum system and the system was pumped downto a pressure below 1e-7 torr. The temperature ramp was then startingusing the temperature controller. The temperature and the massspectrometer signal were recorded using the computer. For a typicalmeasurement with a ramp rate of about 10 degree C. per minute, onecomplete mass scan and one temperature measurement are recorded every 20seconds. The mass spectrum at a given time and temperature at a giventime can be analyzed after the measurement is competed.

EXAMPLES Comparative A

We measured the dielectric constant of a composition similar to Example5 of our International Patent Publication WO 01/78110 and the dielectricconstant was 2.7.

Preparations

Preparation 1—Preparation of Thermosetting Component (referred to hereinas “P1”)

Step (a): Preparation of Mixture of1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A);1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene (shownin FIG. 1C); and at least1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane(shown in FIG. 1C) (collectively “P1 Step (a) Product”)

A first reaction vessel was loaded with adamantane (200 grams),bromobenzene (1550 milliliters), and aluminum trichloride (50 grams).The reaction mixture was heated to 40° C. by a thermostatted water bath.Tert-butyl bromide (1206 grams) was added slowly over a period of 4-6hours to the reaction mixture. The reaction mixture at 40° C. wasstirred overnight.

A second reaction vessel was loaded with 1000 milliliters of aqueoushydrogen chloride (5% w/w). The contents of the first reaction vesselwere gradually discharged into the second reaction vessel whilemaintaining the reaction mixture at 25-35° C. by an external ice bath.An organic phase (dark brown lower phase) was separated and washed withwater (1000 milliliters). About 1700 milliliters of the organic phaseremained.

A third reaction vessel was loaded with 20.4 liters of petroleum ether(mainly isooctane with a boiling range of 80° C.-110° C.). The contentsof the second reaction vessel were slowly added over a period of onehour to the third reaction vessel. The resulting mixture was stirred forat least one hour. The precipitate was filtered off and the filter cakewas washed twice with 300 milliliters per wash of the aforementionedpetroleum ether. The washed filter cake was dried overnight at 45° C. at40 mbar. The P1 Step (a) Product yield was 407 grams dry weight. Thisreaction is shown in FIGS. 1A through 1C as follows. FIG. 1A shows theresulting monomer. FIG. 1B shows the resulting generic dimer and higherproducts while FIG. 1C shows the resulting specific dimer and trimercovered by the FIG. 1B structure.

Analytical techniques including GPC, HPLC, and NMR were used to identifythe product. GPC analysis showed:1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A) had apeak molecular weight of 430;1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene (shownin FIG. 1C) had a peak molecular weight of 820;1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane(shown in FIG. 1C) had a peak molecular weight of about 1150 (shoulder).

Step (b): Preparation of Mixture of1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG.1D);1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F); and at least1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane(shown in FIG. 1F) (collectively “P1 Step (b) Product”)

A first reactor under nitrogen was loaded with toluene (1500milliliters), triethylamine (4000 milliliters), and the P1 Step (a)Product prepared above (1000 grams dry). The mixture was heated to 80°C. and bis-(triphenyl-phosphine)palladium(II)dichloride (i.e.,[Ph₃P]₂PdCl₂) (7.5 grams) and tri-phenylphosphine (i.e. [Ph₃P]) (15grams) were added. After ten minutes, copper(I)iodide (7.5 grams) wasadded.

Over a period of three hours, a solution of phenylacetylene (750 grams)was added to the first reactor. The reaction mixture at 80° C. wasstirred for 12 hours to ensure that the reaction was complete. Toluene(4750 milliliters) was added. The solvent was then distilled off underreduced pressure and a maximum sump temperature and the reaction mixturewas cooled down to about 50° C. The triethylammonium bromide (about 1600milliliters) was filtered off. The filter cake was washed three timeswith 500 milliliters per wash of toluene. The organic phase was washedwith 1750 milliliters of HCl (10 w/w %) and then washed with water (2000milliliters).

To the washed organic phase, water (1000 milliliters), ethylene diaminetetraacetic acid (EDTA) (100 grams), and dimethylglyoxime (20 grams)were added. About 150 milliliters of NH₄OH (25 w/w %) were added toachieve a pH of 9. The reaction mixture was stirred for one hour. Theorganic phase was separated and washed with water (1000 milliliters).With a Dean-Stark trap, azeotropic drying occurred until water evolutionceased. Filtering agent dolomite (100 grams) (tradename Tonsil) wasadded. The mixture was heated to 100° C. for 30 minutes. Dolomite wasfiltered off with a cloth filter having fine pores and the remainder waswashed with toluene (200 milliliters). Silica (100 grams) was added. Thereaction mixture was stirred for 30 minutes. The silica was filtered offwith a cloth filter having fine pores and the remainder was washed withtoluene (200 milliliters). Aqueous NH₃ (20 w/w %), in an amount of 2500milliliters, and 12.5 g of N-acetylcysteine were added. The phases wereseparated. The organic phase was washed with 1000 milliliters of HCl(10% w/w) and then washed two times with 1000 milliliters per wash ofwater. The toluene was distilled off under a reduced pressure of about120 mbar. The pot temperature did not exceed about 70° C. A dark brownviscous oil (1500-1700 milliliters) remained. To the hot mass in thepot, iso-butyl acetate (2500 milliliters) was added and a dark brownsolution formed (4250 milliliters).

A second reactor was loaded with 17000 milliliters of petroleum ether(mainly isooctane with a boiling range of 80° C.-110° C.). The contentsof the first reactor were added over a period of one hour to the secondreactor and stirred overnight. The precipitate was filtered and washedfour times with 500 milliliters per wash of the aforedescribed petroleumether. The product was dried under reduced pressure for four hours at45° C. and five hours at 80° C. The P1 Step (B) Product yield was850-900 grams. This reaction is shown in FIGS. 1D through 1F as follows.FIG. 1D shows the resulting monomer. FIG. 1E shows the resulting genericdimer and higher products while FIG. 1F shows the resulting specificdimer and trimer covered by the FIG. 1F structure.

Analytical techniques including GPC, HPLC, NMR, and FTIR were used toidentify the product. GPC analysis showed:1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG.1D) had a peak molecular weight of about 900;1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F) had a peak molecular weight of about 1500;1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane(shown in FIG. 1F) had a peak molecular weight of about 2100 (shoulder).

The melting point was 164-167° C. From NMR, a multiplet occurred at6,9-8 ppm 2,8+−0,2 H (aromatic part) and 1,7-2,7 ppm 1H+−0,2H (cageportion). From GPC, the ratio of the monomeric and small molecules tooligomeric compounds was 50±5%. FTIR showed the following: PEAKS INCENTIMETERS⁻¹ (PEAK INTENSITY) STRUCTURE 3050 (weak) Aromatic C—H 2930(weak) Aliphatic C—H on adamantane 2200 (very weak) Acetylene 1600 (verystrong) Aromatic C═C 1500 (strong) 1450 (medium) 1350 (medium)LC-MS study showed the presence of peaks:of main monomeric product m/z 840,of its derivatives, m/z 640, 740, 940; 706, 606, 806; 762, 662, 862;938, 838, 1038of dimeric products, m/z 1402, 1302, 1502; 1326, 1226, 1426.

The GPC 3 results follow. Amount Peak Molecular Weight (Weight %)(Relative to PS) Inc Hi Inc ΔR/R Mnmr Mnmr Dmr Trmr Olgmr Mnmr Mnmr DmrTrmr Mnmr w/mnmr 49.3 30.9 10.1 9.7 744 1304 1676 0.10

Preparation 2—Preparation of Thermosetting Component (Referred to Hereinas “P2”)

Step (a): Preparation of Mixture of1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A);1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl] benzene (shownin FIG. 1C); and at least1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane(shownin FIG. 1C)(collectively “P2 Step (a) Product”)

A first reaction vessel was loaded with 1,4-dibromobenzene (587.4 grams)and aluminum trichloride (27.7 grams). This reaction mixture was heatedto 90° C. by a thermostatted water bath and maintained at thistemperature for one hour without stirring and for an additional one hourwith stirring. The reaction mixture was cooled down to 50° C. Adamantane(113.1 grams) was added to the cooled reaction mixture. Over a period offour hours, t-butyl-bromobenzene (796.3 grams) was added to the reactionmixture. The reaction mixture was stirred for an additional 12 hours.

A second reaction vessel was loaded with HCl (566 milliliters, 10%aqueous w/w). The contents of the first reaction vessel at 50° C. weredischarged into the second reaction vessel while maintaining the mixtureat 25-35° C. by an external ice bath. The reaction mass was a lightbrown suspension. The organic phase was a dark brown lower phase andseparated from the reaction mixture. The separated organic phase waswashed with water (380 milliliters). After this washing, about 800milliliters of organic phase remained.

A third reaction vessel was loaded with heptane (5600 milliliters).Slowly over a period of one hour, the contents of the second reactionvessel were added to the third reaction vessel. The suspension wasstirred for at least four hours and the precipitate was filtered off.The filter cake was washed twice with 300 milliliters per wash ofheptane. The P2 Step (a) Product yield was 526.9 grams (wet) and 470.1grams (dry).

Analytical techniques including GPC, HPLC, and NMR were used to identifythe product. GPC analysis showed:1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG. 1A) had apeak molecular weight of about 430;1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl] benzene (shownin FIG. 1C) had a peak molecular weight of about 820;1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane(shown in FIG. 1C) had a peak molecular weight of about 1150 (shoulder).

Step (b): Preparation of Mixture of1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG.1D);1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F); and at least1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane(shown in FIG. 1F)(collectively “P2 Step (b) Product”)

A first reaction pot under nitrogen was loaded with toluene (698milliliters), triethylamine (1860 milliliters), and the P2 Step (a)Product prepared above (465 grams dry). The mixture was heated to 80° C.Palladium-triphenylphosphine complex (i.e. [Ph(PPh₃)₂Cl₂)(4.2 grams) wasadded to the reaction mixture. After waiting ten minutes,triphenylphosphine (i.e., PPh₃)(8.4 grams) was added to the reactionmixture. After waiting another ten minutes, copper(I)-iodide (4.2 grams)was added to the reaction mixture.

Over a period of three hours, a solution of phenylacetylene (348.8grams) was added to the reaction mixture. The reaction mixture at 80° C.was stirred for 12 hours to ensure that the reaction was complete.Toluene (2209 milliliters) was added to the reaction mixture and thendistilled off under reduced pressure and a maximum sump temperature. Thereaction mixture was cooled down to about 50° C. and thetriethylammonium bromide was filtered off. The filter cake was washedtwice with 250 milliliters per wash of toluene. The organic phase waswashed with HCl (10 w/w %)(500 milliliters) and water (500 milliliters).

To the organic phase, water (500 milliliters), EDTA (18.6 grams), anddimethylglyoxime (3.7 grams) were added. NH₄OH (25 w/w %)(about 93milliliters) was added to keep the pH=9. The reaction mixture wasstirred for one hour. The organic phase was separated from the insolublematerial and the emulsion containing the palladium-complex. Theseparated organic phase was washed with water (500 milliliters). With aDean-Stark trap, azeotropic drying of the washed organic phase occurreduntil water evolution ceased. Filtering agent dolomite (tradenameTonsil)(50 grams) was added and the reaction mixture was heated to 100°C. for 30 minutes. The dolomite was filtered off with a cloth filterhaving fine pores and the organic material was washed with toluene (200milliliters). Silica (50 grams) was added and the reaction mixture wasstirred for 30 minutes. The silica was filtered off with a cloth filterhaving fine pores and the organic material was washed with toluene (200milliliters). Aqueous NH₃ (20% w/w)(250 milliliters) andN-acetylcysteine (12.5 grams) were added. The phases were separated. Theorganic phase was washed with HCl(10% w/w)(500 milliliters). The organicmaterial was washed twice with 500 milliliters per wash of water. Thetoluene was distilled off under reduced pressure of about 120 mbar. Thepot temperature did not exceed 70° C. A dark brown viscous oil (about500-700 milliliters) remained. To the hot mass in the pot, iso-butylacetate (1162 milliliters) was added. A dark brown solution (about 1780milliliters) formed.

A second reaction pot was loaded with heptane (7120 milliliters). Over aperiod of one hour, the contents of the first reaction pot were added tothe second reaction pot. The precipitate was stirred for at least threehours and filtered off. The product was washed four times with 250milliliters per wash of heptane. The product was dried under reducedpressure of 40 mbar at 80° C. The P2 Step (b) Product yield was 700grams wet or 419 grams dry.

Analytical techniques including GPC, HPLC, and NMR were used to identifythe product. GPC analysis showed:1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG.1D) had a peak molecular weight of about 900;1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F) had a peak molecular weight of about 1500;1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane(shown in FIG. 1F) had a peak molecular weight of about 2100 (shoulder).

The melting point was 164-167° C. From NMR, a multiplet occurred at6,9-8 ppm 2,8+−0,2H (aromatic part) and 1,7-2,7 ppm 1H+−0,2H (cageportion). From GPC, the ratio of the monomeric and small molecules tooligomeric compounds was 50±5%. FTIR showed the following: PEAKS INCENTIMETERS⁻¹ (PEAK INTENSITY) STRUCTURE 3050 (weak) Aromatic C—H 2930(weak) Aliphatic C—H on adamantane 2200 (very weak) Acetylene 1600 (verystrong) Aromatic C═C 1500 (strong) 1450 (medium) 1350 (medium)LC-MS study showed the presence of peaks:of main monomeric product m/z 840,of its derivatives, m/z 640, 740, 940; 706, 606, 806; 762, 662, 862;938, 838, 1038of dimeric products, m/z 1402, 1302, 1502; 1326, 1226, 1426.

GPC 3 results follow. Amount Peak Molecular Weight (Weight %) (Relativeto PS) Inc Hi Inc ΔR/R Mnmr Mnmr Dmr Trmr Olgmr Mnmr Mnmr Dmr Trmr Mnmr7.7 36.4 26.8 12.3 16.8 546 763 1328 1672 0.14Preparation 3

Impact of Solvent on ratio of1,3,5,7-tetrakis[3′,4′-(phenylethynyl)phenyl]adamantane (shown in FIG.1D) to1,3/4-bis{1′,3′,5′-tris[3″/4″-phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F) and at least1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane (shown in FIG. 1F)

850 milliliters of P1 Step (a) Product was divided into four equalparts, and subjected to precipitation in petroleum ether, ligroine,heptane, and methanol. Each part was precipitated into 2520 ml of thesolvent, vacuum filtered (Büchner funnel diam. 185 mm), washed on filtertwice by 150 ml of the solvent, then dried in a vacuum oven for twohours at about 20° C., overnight at 40° C., and at 70-80° C. to constantweight.

Precipitation into hydrocarbons resulted in very dispersed light beigepowders that dried without complications. Precipitation into methanolgave heavy, brownish granular solid (particles size approximately 1 mm),which formed tar when dried at 20° C. This product was dried further.

Reaction mixtures were analyzed by GPC during the reaction and beforeprecipitation. All filtrates and final solids were analyzed by GPC andthe results are in Table 4. In Table 4, PPT stands for precipitation,monomer is 1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane (shown in FIG.1A); dimer is1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene (shownin FIG. 1C); and trimer is1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis(3″″/4″″-bromophenyl)adamantane(shown in FIG. 1C). TABLE 4 Peak Ratio [monomer to Peak Ratio [monomerto (dimer + trimer)] (dimer + trimer)] before PPT Solvent For PPT afterPPT 75.0:25.0 Petroleum Ether 52.5:47.4 75.0:25.0 Ligroine 64.0:36.075.0:25.0 Heptane 66.2:33.8 75.0:25.0 Methanol 75.0:25.0

To summarize these results, the peak ratio of monomer to (dimer+trimer)in the reaction mixture was about 3:1. The product lost in hydrocarbonsprecipitation filtrates was mostly (>90%) monomer while losses inwashing filtrates were negligible. There is no product in methanolprecipitation filtrates. The monomer to (dimer+trimer) ratio afterprecipitation increases (1:1→3:1), and monomer losses in the filtratesdecrease (56→0%) in the sequence: petroleum ether, ligroine, heptane,and methanol.

Preparation 4—Preparation of Thermosetting Component

The1,3/4-bis{1′,3′,5′-tris[3″/4″-(phenylethynyl)phenyl]adamant-7′-yl}benzene(shown in FIG. 1F) in the Preparation 1 product mixture is separatedusing preparative liquid chromatography (PLC). PLC is similar to theHPLC method described above but uses larger columns to separate largerquantities of the mixture (from several grams to several hundred grams).

Preparation 5—Preparation of Thermosetting Component

The1,3-bis{3′/4′-[1″,3″,5″-tris[3′″/4′″-(phenylethynyl)phenyl]adamant-7″-yl]phenyl}-5,7-bis[3″″/4″″-(phenylethynyl)phenyl]adamantane(shown in FIG. 1F) in the Preparation 1 product mixture is separatedusing preparative liquid chromatography (PLC).

Preparation 6—Preparation of Thermosetting Component

The diamantane monomer of Formula V and oligomer or polymer ofdiamantane monomer of Formulae VI, VIII, X, XII, XV, XVI, and XVIII areprepared using the following method. As shown in FIG. 2, diamantane isconverted using bromine and a Lewis Acid catalyst to brominateddiamantane product. The brominated diamantane product is then reactedwith bromobenzene in the presence of a Lewis Acid catalyst to formbromophenylated diamantane. The bromophenylated diamantane is thenreacted with a terminal alkyne in the presence of a catalyst system asused in the so-called Sonogashira coupling reaction. The product at eachstep is worked up as described in our pending patent applicationPCT/US01/22204 filed Oct. 17, 2001.

Preparation 7—Preparation of Thermosetting Component (a)

The diamantane monomer of Formula V and oligomer or polymer ofdiamantane monomer of Formulae VI, VIII, X, XII, XV, XVI, and XVIII areprepared using the following method. As shown in FIGS. 1A through 1F,diamantane is converted to the bromophenylated compositions ofdiamantane using similar synthetic procedures as described inPreparations 1 and 2. In FIGS. 1A through 1C, diamantane is reacted witha substituted halogen phenyl compound in the presence of a Lewis Acidcatalyst as described in Preparations 1 and 2, and/or a second catalystcomponent as described in Preparation 2. A mixture of monomers, dimers,trimers, and higher oligomers is obtained after work-up of the reactionmixtures. In FIGS. 1D through 1F, the bromophenylated diamantane mixtureis then reacted with a terminal alkyne in the presence of catalyst toproduce the alkyne-substituted diamantane compositions of the presentinvention.

Inventive Example 1

In this example, the ethynyl containing group is first reacted with thethermosetting component.

To a 500-mL, 3 neck flask equipped with a condenser, a mechanicalstirrer and a nitrogen inlet-outlet were added thermosetting componentsimilar to Preparation 1 or 2 above (amount=20.00 grams (20.19millimoles)); dichlorobis(triphenylphosphine)palladium(II)(amount=1.134grams (1.62 millimoles)); triphenylphosphine (amount=0.848 gram (3.23millimoles)); copper(I) iodide (amount=0.308 gram (1.62 millimoles));triethylamine (amount=70 milliliters); and toluene (amount=80milliliters). The mixture was heated to 80° C. and 4-ethynylaniline(amount=0.63 gram (5.2 millimoles)) in 20 milliliters of triethylaminewere added to the reaction mixture dropwise. The reaction mixture washeated at 80° C. for 8 hours and then phenylacetylene (amount=16.50grams (161.6 millimoles)) and triethylamine (amount=20 milliliters) wereadded to the reaction mixture dropwise. The solution was heated at 80°C. for 8 hours.

The reaction mixture was cooled to room temperature and transferred to a1 liter, 3 neck flask equipped with a condenser, a mechanical stirrerand a nitrogen inlet-outlet and toluene (100 milliliters) was added. Thesolution was then neutralized with 6N HCl. The resulting water wasremoved. The toluene solution was then stirred with 100 mL of 6N HCl at60° C. for 30 minutes. The mixture was filtered through celite®naturally occurring inorganic material. The aqueous solution was thenremoved. The HCl extraction was repeated for two more times. The toluenesolution was then washed with 100 mL of deionized water twice. Thesolution was stirred with 100 mL of 0.1M of N-acetyl-cysteine in ammoniasolution at 60° C. for 30 min. The aqueous solution was then removed.The ammonia extraction was repeated for five more times. The toluene wasthen removed by rotary evaporator and the resulting solid was driedunder vacuum overnight to yield 17.10 grams (85.05%) of reddish solid(called Solid A).

To a 100-mL, 3 neck flask equipped with a condenser, a magnetic stirrerand a nitrogen inlet-outlet were added 20.70 mg (60% dispersion inmineral oil, which corresponds to 0.5176 mmol) of sodium hydride, and 20ml of hexane. The mixture was stirred at room temperature for 5 minutesand upper hexane layer was decanted. To the above mixture were addedtetrahydrofuran (amount=20 millilters)(THF) and 1.00 g of the aboveSolid A. The mixture was stirred at room temperature for 30 minutes andthen epoxy functionalized polynorbornene (amount=0.6540 gram) was added.The solution was then heated at 65° C. for 12 hours. THF was thenremoved by rotary evaporator and the resulting mixture was dissolve in15 ml of xylene (called Solution B). This solution was washed byde-ionized water for 3 times. The preceding reaction scheme is shown inFIG. 12 where although only1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene isshown, it is understood that similar reactions occur for1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane and1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis{3″″/4″″-bromophenyl)adamantane.

To a 65-mL plastic bottle was added the above Solution B andortho-cresol novolac (amount=0.030 gram; molecular weight of 1760;supplied by Schenectady International Inc.). The solution was stirred atroom temperature for 1 hour. The solution was then filtered through a0.1 μm teflon filter.

The composition was applied to a substrate using typical coatingconditions known to those skilled in the art. The resulting spun-oncomposition was baked for one minute under N₂ (<50 ppm 02) at each ofthe following temperatures: 125° C., 250° C., and 300° C. The furnacecure condition was 400° C. for 60 minutes in N₂ (26 liters/minute) withramping up from 250° C. at 5° K per minute. The cure temperature rangewas from 350° C. to 450° C. In each composition, the porogen decomposedand the decomposed porogen volatilized whereby pores formed in thecomposition. The layer had a refractive index of 1.433 and a thicknessof 2414 Angstroms. FIG. 13 shows the Scanning Electronic Microscoperesults.

Inventive Example 2

In this example, the ethynyl containing group is first reacted with theporogen.

To a 500-milliliter, 3 neck flask equipped with a condenser, a magneticstirrer and a nitrogen inlet-outlet were added sodium hydride(amount=0.262 gram (60% dispersion in mineral oil, which corresponds to6.54 millimoles)), and hexane (amount=60 milliliters). The mixture wasstirred at room temperature for 5 minutes and the upper hexane layer wasdecanted. To the above mixture were added 4-ethynylaniline (amount=0.695gram (5.93 millimoles)) and tetrahydrofuran (THF, amount=144 grams). Thesolution was stirred at room temperature for 1 hour and epoxyfunctionalized polynorbornene (amount=15 grams) was added. The reactionmixture was heated at 60° C. for 12 hours. THF was then removed byrotary evaporator and the resulting mixture was dissolve in 50 ml oftoluene to form a solution (referred to below as Solution A).

To a 500-milliliter, 3 neck flask equipped with a condenser, amechanical stirrer and a nitrogen inlet-outlet were added thermosettingcomponent similar to Preparation 1 or 2 above (amount=25.75 grams (26.00millimoles)), dichlorobis(triphenylphosphine)palladium(II) (amount=1.461grams(2.081 millimoles)), triphenylphosphine (amount=1.092 gram(4.162millimoles)), copper(I) iodide (amount=0.3963 gram(2.081 millimoles)),triethylamine (amount=160 milliliters), and toluene (amount=80milliliters). The mixture was heated to 80° C. and the above Solution Awas added to the reaction mixture dropwise. The reaction mixture washeated at 80° C. for 12 hours and then phenylacetylene (amount=21.3grams (208.1 millimoles)) and toluene (amount=30 milliliters) were addedto the reaction mixture dropwise. The solution was heated at 80° C. for4 hours.

The reaction mixture was cooled to room temperature and transferred to a1 liter, 3 neck flask equipped with a condenser, a mechanical stirrerand a nitrogen inlet-outlet and toluene (amount=100 milliliters) wasadded. The solution was then neutralized with 6N HCl. The resultingwater was removed. The toluene solution was then stirred with 100 mL of6N HCl at 60° C. for 30 min. The mixture was filtered through celite®naturally occurring inorganic material. The aqueous solution was thenremoved. The HCl extraction was repeated for two more times. The toluenesolution was then washed with 100 mL of deionized water twice. Thesolution was stirred with 100 mL of 0.1M of N-acetyl-cysteine in ammoniasolution at 60° C. for 30 min. The aqueous solution was then removed.The ammonia extraction was repeated for five more times. The toluene wasthen removed by rotary evaporator and the resulting solid was driedunder vacuum overnight. The preceding reaction scheme is shown in FIG.14 where although only1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene isshown, it is understood that similar reactions occur for1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane and1,3-bis{3′/4′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis{3″″/4″″-bromophenyl)adamantane.

To a 125-milliliter plastic bottle were added 4.48 g of the above solid,0.047 g of ortho-cresol novolac (amount=0.047 gram; molecular weight of1760; supplied by Schenectady International Inc.) and xylenes (40.74grams). The solution was stirred at room temperature for 1 hour. Thesolution was then filtered through a 0.1 μm teflon filter.

The composition was applied to a substrate using typical coatingconditions known to those skilled in the art. The resulting spun-oncomposition was baked for one minute under N₂ (<50 ppm O₂) at each ofthe following temperatures: 125° C., 250° C., and 300° C. The furnacecure condition was 400° C. for 60 minutes in N₂ (26 liters/minute) withramping up from 250° C. at 5° K per minute. The cure temperature rangewas from 350° C. to 450° C. In each composition, the porogen decomposedand the decomposed porogen volatilized whereby pores formed in thecomposition. After bake, the layer had a refractive index of 1.636 and athickness of 1255 Angstroms. After cure, the layer had a refractiveindex of 1.398 and a thickness of 1056 Angstroms. FIG. 15 shows ScanningElectron Microscope results.

Inventive Example 3

In this example, the ethynyl containing group is first reacted with theporogen.

To a 300-milliliter, 3 neck flask equipped with a condenser, a magneticstirrer and a nitrogen inlet-outlet were added triphenylphosphine(amount=9.76 grams (37.2 millimoles)), diethyl azodicarboxylate(amount=6.49 grams (37.2 millimoles)), 3-hydroxyphenylacetylene(amount=4.00 grams (33.9 millimoles)), and tetrahydrofuran (THF;amount=90 milliliters). A clear solution was obtained after the mixturewas stirred at room temperature for 5 minutes. To this solution was thenadded 10.76 g of polycaprolactone in 40 ml of THF solution dropwise atroom temperature. The solution was stirred at room temperature for 12hours. THF was then partially removed by rotary evaporator to make a 40ml viscous solution and ethyl ether (amount=50 milliliters) was added tothe mixture and put into refrigerator for 30 min. The precipitate thatformed was removed by filtration. Ethyl ether in the filtrate was thenremoved by rotary evaporator. To this viscous solution was addedmethylene chloride (50 milliliters) and put into refrigerator overnight.The precipitation that formed was removed by filtration. The solvent wasthen removed by rotary evaporator to yield a viscous liquid (referred tobelows as Liquid A).

To a 500-mL, 3 neck flask equipped with a condenser, a mechanicalstirrer and a nitrogen inlet-outlet were added thermosetting componentsimilar to Preparation 1 or 2 above (amount=13.34 grams (13.47millimoles)), dichlorobis(triphenylphosphine)palladium(II)(amount=0.7566gram(1.078 millimoles)), triphenylphosphine(amount=0.5655gram(2.156 millimoles), copper(I) iodide(amount=0.2053gram(1.078 millimoles), triethylamine (amount=110milliliters). The mixture was heated to 80° C. and 12.30 g of the aboveLiquid A with toluene (amount=40 milliliters) was added to the reactionmixture dropwise. The reaction mixture was heated at 80° C. for 12 hoursand then 10.32 g (101.1 mmol) of phenylacetylene and toluene (amount=30milliliters) were added to the reaction mixture dropwise. The solutionwas heated at 80° C. for 4 hours.

The reaction mixture was cooled to room temperature and transferred to a1 liter, 3 neck flask equipped with a condenser, a mechanical stirrerand a nitrogen inlet-outlet and toluene (amount=100 milliliters) wasadded. The solution was then neutralized with 6N HCl. The resultingwater was removed. The toluene solution was then stirred with 100 mL of6N HCl at 60° C. for 30 min. The mixture was filtered through celite®.The aqueous solution was then removed. The HCl extraction was repeatedfor two more times. The toluene solution was then washed with 100 mL ofdeionized water twice. The solution was stirred with 100 mL of 0.1M ofN-acetyl-cysteine in ammonia solution at 60° C. for 30 min. The aqueoussolution was then removed. The ammonia extraction was repeated for fivemore times. The toluene was then removed by rotary evaporator and theresulting solid was dried under vacuum overnight. The preceding reactionscheme is shown in FIG. 16 where although only1,3/4-bis[1′,3′,5′-tris(3″/4″-bromophenyl)adamant-7′-yl]benzene isshown, it is understood that similar reactions occur for1,3,5,7-tetrakis(3′/4′-bromophenyl)adamantane and1,3-bis{3′/14′-[1″,3″,5″-tris(3′″/4′″-bromophenyl)adamant-7″-yl]phenyl}-5,7-bis{3″″/4″″-bromophenyl)adamantane.

To a 125-milliliter plastic bottle were added 2 grams of the abovesolid, polycarbosilane (CH₂SiH₂)_(q) where q is 20-30 (amount=0.1334gram; supplied by Starfire Systems, Inc.) and 20 g of xylenes (amount=20grams). The solution was heated at 145° C. for 15.5 hours. The solutionwas then filtered through a 0.1 μm teflon filter.

The composition was applied to a substrate using typical coatingconditions known to those skilled in the art. The resulting spun-oncomposition was baked for one minute under N₂ (<50 ppm O₂) at each ofthe following temperatures: 125° C., 250° C., and 300° C. The furnacecure condition was 400° C. for 60 minutes in N₂ (26 liters/minute) withramping up from 250° C. at 5° K per minute. The cure temperature rangewas from 350° C. to 450° C. In each composition, the porogen decomposedand the decomposed porogen volatilized whereby pores formed in thecomposition. After bake, the layer had a refractive index of 1.617 and athickness of 5640 Angstroms. After cure, the layer had a refractiveindex of 1.593 and a thickness of 3784 Angstroms. The above formulationwithout the adhesion promoter had an after base refractive index of1.639, an after bake thickness of 1369 Angstroms, an after curerefractive index of 1.584, an after cure thickness of 993 Angstroms, adegassed dielectric constant of 2.66, and an additional cure refractiveindex of 1.562.

1. A composition comprising: (a) thermosetting component comprising: (1)optionally monomer of Formula I

and (2) at least one oligomer or polymer of Formula II

where said E is a cage compound; each of said Q is the same or differentand selected from aryl, branched aryl, and substituted aryl wherein saidsubstituents include hydrogen, halogen, alkyl, aryl, substituted aryl,heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl,hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; saidG is aryl or substituted aryl where substituents include halogen andalkyl; said h is from 0 to 10; said i is from 0 to 10; said j is from 0to 10; and said w is 0 or 1; (b) porogen that bonds to saidthermosetting component (a).
 2. The composition of claim 1 wherein saidthermosetting component (a) is functionalized.
 3. The composition ofclaim 2 wherein said functionality is selected from the group consistingof acetylene; 4-ethynylaniline; 3-hydroxyphenylacetylene;4-fluorophenylacetylene; and 1-ethylcyclohexylamine.
 4. The compositionof claim 1 wherein said porogen comprises a material having adecomposition temperature less than the glass transition temperature ofsaid thermosetting component (a) and greater than the curing temperatureof said thermosetting component (a).
 5. The composition of claim 4wherein said porogen is selected from the group consisting ofunsubstituted polynorbornene, substituted polynorbornene,polycaprolactone, unsubstituted polystyrene, substituted polystyrene,polyacenaphthylene homopolymer, and polyacenaphthylene copolymer.
 6. Thecomposition of claim 5 wherein said porogen is functionalized.
 7. Thecomposition of claim 6 wherein said functionality is selected from thegroup consisting of epoxy, hydroxy, carboxylic acid, amino, and ethynyl.8. The composition of claim 1 wherein said porogen is covalently bondedto said thermosetting component (a).
 9. The composition of claim 8wherein said porogen is covalently bonded to said thermosettingcomponent (a) through an ethynyl containing group.
 10. The compositionof claim 9 wherein said ethynyl containing group is acetylene.
 11. Thecomposition of claim 8 wherein said thermosetting component (a)comprises (1) adamantane monomer of Formula III

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

where said h is from 0 to 10; said i is from 0 to 10; said j is from 0to 10; each of said R₁ is the same or different and selected fromhydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, arylether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl,hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; and each of saidY is same or different and is selected from hydrogen, alkyl, aryl,substituted aryl, or halogen.
 12. The composition of claim 11 whereinsaid monomer is present.
 13. The composition of claim 11 or 12 whereinsaid R₁ is aryl or substituted aryl and said Y is hydrogen, phenyl, orbiphenyl.
 14. The composition of claim 13 wherein said (2) adamantaneoligomer or polymer is dimer of Formula IX

or said (2) diamantane oligomer or polymer is dimer of Formula X


15. The composition of claim 13 wherein said (2) adamantane oligomer orpolymer is trimer of Formula XI

or said (2) diamantane oligomer or polymer is trimer of Formula XII


16. The composition of claim 13 where in said thermosetting component(a), said oligomer or polymer (2) comprises a mixture of adamantanedimer of Formula IX

and adamantane trimer of Formula XI

or diamantane dimer of Formula X

and diamantane trimer of Formula XII


17. The composition of claim 16 where in said thermosetting component(a), said monomer (1) and said oligomer or polymer (2) are adamantanebased monomers.
 18. The composition of claim 17 wherein at least two ofsaid R₁C≡C groups on said phenyl groups are two different isomers and atleast one of said phenyl groups between two bridgehead carbons of saidadamantane monomers exists as two different isomers.
 19. The compositionof claim 18 wherein said at least two isomers are meta- andpara-isomers.
 20. The composition of claim 13 additionally comprising(c) adhesion promoter comprising compound having at leastbifunctionality wherein the bifunctionality may be the same or differentand at least one of said bifunctionality is capable of interacting withsaid thermosetting component (a).
 21. The composition of claim 20wherein said adhesion promoter is selected from the group consisting of:silanes of the Formula XXIV: (R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n) whereinR₂, R₃, R₄, and R₅ each independently represents hydrogen, hydroxyl,unsaturated or saturated alkyl, substituted or unsubstituted alkyl wherethe substituent is amino or epoxy, unsaturated or saturated alkoxyl,unsaturated or saturated carboxylic acid radical, or aryl, at least twoof said R₂, R₃, R₄, and R₅ represent hydrogen, hydroxyl, saturated orunsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acidradical, and k+l+m+n≦4; polycarbosilane of the Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted orunsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene;R₉, R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆ each independently represents hydrogenatom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene andmay be linear or branched, R₁₃ represents organosilicon, silanyl,siloxyl, or organo group, and p, q, r, and s satisfy the conditions of[4≦p+q+r+s≦100,000], and q and r and s may collectively or independentlybe zero; glycidyl ethers, or esters of unsaturated carboxylic acidscontaining at least one carboxylic acid group; vinyl cyclic oligomers orpolymers where the cyclic group is vinyl, aromatic, or heteroaromatic;and phenol-formaldehyde resins or oligomers of the Formula XXVI:—[R₁₈C₆H₂(OH)(R₁₉)]_(t)— where R₁₈ is substituted or unsubstitutedalkylene, cycloalkylene, vinyl, allyl, or aryl, R₁₉ is alkyl, alkylene,vinylene, cycloalkylene, allylene, or aryl, and t=3-100.
 22. Thecomposition of claim 21 wherein said adhesion promoter (c) is saidphenol-formaldehyde resin or oligomer.
 23. An oligomer comprising saidcomposition of claim
 20. 24. A spin-on precursor comprising saidoligomer of claim 23 and solvent.
 25. A thermosetting matrix made fromsaid spin-on precursor of claim
 24. 26. A layer comprising saidthermosetting matrix of claim
 25. 27. The layer of claim 26 wherein saidthermosetting matrix is cured.
 28. The layer of claim 26 wherein saidlayer has a dielectric constant of less than 2.7, preferably less than2.5, preferably less than 2.2, and preferably less than 2.0.
 29. Thelayer of claim 26 wherein said layer has an average pore size diameterof less than 20 nanometers.
 30. A substrate having thereon at least oneof said layer of claim
 26. 31. A microchip comprising said substrate ofclaim
 30. 32. A method of lowering the dielectric constant of acomposition comprising (a) thermosetting component comprising: (1)optionally monomer of Formula I

and (2) at least one oligomer or polymer of Formula II

where said E is a cage compound; each of said Q is the same or differentand selected from aryl, branched aryl, and substituted aryl wherein saidsubstituents include hydrogen, halogen, alkyl, aryl, substituted aryl,heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl,hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; saidG is aryl or substituted aryl where substituents include halogen andalkyl; said h is from 0 to 10; said i is from 0 to 10; said j is from 0to 10; and said w is 0 or 1; (b) adhesion promoter comprising compoundhaving at least bifunctionality wherein the bifunctionality may be thesame or different and the first functionality is capable of interactingwith said thermosetting component (a) and the second functionality iscapable of interacting with a substrate when said composition is appliedto said substrate comprising the steps of: bonding porogen to saidthermosetting component; decomposing said bonded porogen; andvolatilizing said porogen whereby pores form in said composition. 33.The method of claim 32 wherein said thermosetting component (a) isfunctionalized.
 34. The method of claim 33 wherein said thermosettingcomponent functionality is selected from the group consisting ofacetylene; 4-ethynylaniline; 3-hydroxyphenylacetylene;4-fluorophenylacetylene; and 1-ethylcyclohexylamine.
 35. The method ofclaim 32 wherein said porogen comprises a material having adecomposition temperature less than the glass transition temperature ofsaid thermosetting component (a) and greater than the curing temperatureof said thermosetting component (a).
 36. The method of claim 35 whereinsaid porogen is selected from the group consisting of unsubstitutedpolynorbornene, substituted polynorbornene, polycaprolactone,unsubstituted polystyrene, substituted polystyrene, polyacenaphthylenehomopolymer, and polyacenaphthylene copolymer.
 37. The method of claim36 wherein said porogen is functionalized.
 38. The method of claim 37wherein said porogen functionality is selected from the group consistingof epoxy, hydroxy, carboxylic acid, amino, and ethynyl.
 39. The methodof claim 32 wherein said porogen is covalently bonded to saidthermosetting component (a).
 40. The method of claim 39 wherein saidporogen is covalently bonded to said thermosetting component (a) throughan ethynyl containing group.
 41. The method of claim 40 wherein saidethynyl containing group is acetylene.
 42. The method of claim 39wherein said thermosetting component (a) comprises (1) adamantanemonomer of Formula III

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

where said h is from 0 to 10; said i is from 0 to 10; said j is from 0to 10; each of said R₁ is the same or different and selected fromhydrogen, halogen, alkyl, aryl, substituted aryl, heteroaryl, arylether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl,hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; and each of saidY is same or different and is selected from hydrogen, alkyl, aryl,substituted aryl, or halogen.
 43. The method of claim 42 wherein saidmonomer is present.
 44. The method of claim 42 or 43 wherein saiddecomposing said porogen step comprises curing by furnace, hot plate,electron beam radiation, microwave radiation, or ultraviolet radiation.45. The method of claim 44 wherein said R₁ is aryl or substituted aryland said Y is hydrogen, phenyl, or biphenyl.
 46. The method of claim 45wherein said (2) adamantane oligomer or polymer is dimer of Formula IX

or said (2) diamantane oligomer or polymer is dimer of Formula X


47. The method of claim 45 wherein said (2) adamantane oligomer orpolymer is trimer of Formula XI

or said (2) diamantane oligomer or polymer is trimer of Formula XII


48. The method of claim 45 where in said thermosetting component (a),said oligomer or polymer (2) comprises a mixture of adamantane dimer ofFormula IX

and adamantane trimer of Formula XI

or diamantane dimer of Formula X

and diamantane trimer of Formula XII


49. The method of claim 48 where in said thermosetting component (a),said monomer (1) and said oligomer or polymer (2) are adamantane basedmonomers.
 50. The method of claim 49 wherein at least two of said R₁C≡Cgroups on said phenyl groups are two different isomers and at least oneof said phenyl groups between two bridgehead carbons of said adamantanemonomers exists as two different isomers.
 51. The method of claim 50wherein said at least two isomers are meta- and para-isomers.
 52. Themethod of claim 44 wherein at least one of said first functionality andsaid second functionality of said adhesion promoter (b) is selected fromthe group consisting of Si containing groups; N containing groups; Cbonded to O containing groups; hydroxyl groups; and C double bonded to Ccontaining groups.
 53. The method of claim 52 wherein said Si containinggroup is selected from silanes of the Formula XXIV:(R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n) wherein R₂, R₃, R₄, and R₅ eachindependently represents hydrogen, hydroxyl, unsaturated or saturatedalkyl, substituted or unsubstituted alkyl where the substituent is aminoor epoxy, unsaturated or saturated alkoxyl, unsaturated or saturatedcarboxylic acid radical, or aryl, at least two of said R₂, R₃, R₄, andR₅ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl,unsaturated alkyl, or unsaturated carboxylic acid radical, andk+l+m+n≦4; or polycarbosilane of the Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted orunsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene;R₉, R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆ each independently represents hydrogenatom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene andmay be linear or branched, R₁₃ represents organosilicon, silanyl,siloxyl, or organo group, and p, q, r, and s satisfy the conditions of[4≦p+q+r+s≦100,000], and q and r and s may collectively or independentlybe zero; said C bonded to O containing groups are selected from glycidylethers, or esters of unsaturated carboxylic acids containing at leastone carboxylic acid group; said C double bonded to C containing groupsis vinyl cyclic oligomers or polymers where the cyclic group is vinyl,aromatic, or heteroaromatic; and said hydroxyl group isphenol-formaldehyde resins or oligomers of the Formula XXVI:—[R₁₈C₆H₂(OH)(R₁₉)]_(t)— where R₁₈ is substituted or unsubstitutedalkylene, cycloalkylene, vinyl, allyl, or aryl, R₁₉ is alkyl, alkylene,vinylene, cycloalkylene, allylene, or aryl, and t=3-100.
 54. The methodof claim 53 wherein said adhesion promoter (c) is saidphenol-formaldehyde resin or oligomer. and at least one oligomer orpolymer, wherein the at least one oligomer or polymer comprises at leastone cage compound in the backbone of the at least one oligomer orpolymer and further comprises at least one aryl, substituted aryl orbranched aryl; and a porogen that bonds to the thermosetting component.56. The composition of claim 55, wherein the cage compound comprises anadamantane or a diamantane compound.
 57. The composition of claim 56,wherein the cage compound comprises an adamantane compound.
 58. Thecomposition of claim 55, wherein the at least one oligomer or polymercomprises the structure of Formula II:

where said E is the cage compound; each of said Q is the same ordifferent and selected from aryl, branched aryl, and substituted arylwherein said substituents include hydrogen, halogen, alkyl, aryl,substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl,hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, orcarboxyl; said G is aryl or substituted aryl where substituents includehalogen and alkyl; said h is from 0 to 10; said i is from 0 to 10; saidj is from 0 to 10; and said w is 0 or
 1. 59. The composition of claim55, further comprising an adhesion promoter.
 60. The composition ofclaim 55, wherein the thermosetting component comprises the adamantanemonomer of formula III:

or polymer of Formula IV:

the diamantane monomer of Formula V:

or the diamantane oligomer or polymer of Formula VI

where h is from 0 to 10; i is from 0 to 10; j is from 0 to 10; each ofR₁ is the same or different and selected from hydrogen, halogen, alkyl,aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,hydroxyl, or carboxyl; and each of said Y is same or different and isselected from hydrogen, alkyl, aryl, substituted aryl, or halogen. 61.The composition of claim 55, wherein the thermosetting composition isfunctionalized.
 62. The composition of claim 61, wherein thefunctionality comprises acetylene; 4-ethynylaniline;3-hydroxyphenylacetylene; 4-fluorophenylacetylene or1-ethylcyclohexylamine.
 63. The composition of claim 55, wherein theporogen comprises a material having a decomposition temperature lessthan the glass transition temperature of the thermosetting component.64. The composition of either of claims 55 or 63, wherein the porogencomprises a material having a decomposition temperature greater than thecuring temperature of the thermosetting component.
 65. The compositionof claim 55, wherein the porogen comprises an unsubstitutedpolynorbornene, substituted polynorbornene, polycaprolactone,unsubstituted polystyrene, substituted polystyrene, polyacenaphthylenehomopolymer or polyacenaphthylene copolymer.
 66. The composition ofeither of claims 55 or 65, wherein the porogen is functionalized. 67.The composition of claim 66, wherein the functionality comprises epoxy,hydroxy, carboxylic acid, amino or ethynyl.
 68. The composition of claim55, wherein the porogen is covalently bonded to the thermosettingcomponent.
 69. The composition of claim 68, wherein the porogen iscovalently bonded to the thermosetting component through anethynyl-containing group.
 70. The composition of claim 69, wherein theethynyl-containing group is acetylene.
 71. The composition of claim 55,wherein the monomer is present in the thermosetting composition.
 72. Thecomposition of claim 60, wherein said R₁ is aryl or substituted aryl andsaid Y is hydrogen, phenyl, or biphenyl.
 73. The composition of claim55, wherein the at least one oligomer or polymer comprises the structureof Formula IX

or the structure of Formula X:


74. The composition of claim 55, wherein the at least one oligomer orpolymer comprises the structure of Formula XI:

or the structure of Formula XII:


75. The composition of claim 55, wherein the thermosetting componentcomprises a mixture of the compound of Formula IX

and Formula XI

or Formula X

and Formula XII


76. The composition of claim 75, wherein the thermosetting component,the monomer and the at least one oligomer or polymer compriseadamantane-based monomers.
 77. The composition of claim 76, wherein atleast two of the R₁C≡C groups on the phenyl groups are two differentisomers and at least one of the phenyl groups between two bridgeheadcarbons of the adamantane-based monomers exists as two differentisomers.
 78. The composition of claim 77, wherein the at least twoisomers are meta- and para-isomers.
 79. The composition of claim 59,wherein the adhesion promoter comprises a compound having at leastbifunctionality wherein the bifunctionality may be the same or differentand at least one of said bifunctionality is capable of interacting withsaid thermosetting component.
 80. The composition of claim 79 whereinsaid adhesion promoter comprises at least one of the following: silanesof the Formula XXIV: (R₂)_(k)(R₃)_(l)Si(R₄)_(m)(R₅)_(n) wherein R₂, R₃,R₄, and R₅ each independently represents hydrogen, hydroxyl, unsaturatedor saturated alkyl, substituted or unsubstituted alkyl where thesubstituent is amino or epoxy, unsaturated or saturated alkoxyl,unsaturated or saturated carboxylic acid radical, or aryl, at least twoof said R₂, R₃, R₄, and R₅ represent hydrogen, hydroxyl, saturated orunsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acidradical, and k+l+m+n<4; polycarbosilane of the Formula XXV:

in which R₈, R₁₄, and R₁₇ each independently represents substituted orunsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene;R₉, R₁₀, R₁₁, R₁₂, R₁₅, and R₁₆ each independently represents hydrogenatom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene andmay be linear or branched, R₁₃ represents organosilicon, silanyl,siloxyl, or organo group, and p, q, r, and s satisfy the conditions of[4<p+q+r+s≦100,000], and q and r and s may collectively or independentlybe zero; glycidyl ethers, or esters of unsaturated carboxylic acidscontaining at least one carboxylic acid group; vinyl cyclic oligomers orpolymers where the cyclic group is vinyl, aromatic, or heteroaromatic;and phenol-formaldehyde resins or oligomers of the Formula XXVI:—[R₁₈C₆H₂(OH)(R₁₉)]_(t)— where R₁₈ is substituted or unsubstitutedalkylene, cycloalkylene, vinyl, allyl, or aryl, R₁₉ is alkyl, alkylene,vinylene, cycloalkylene, allylene, or aryl, and t=3-100.
 81. Thecomposition of claim 80, wherein the adhesion promoter is saidphenol-formaldehyde resin or oligomer.
 82. An oligomer comprising thecomposition of claim
 79. 83. A spin-on precursor comprising the oligomerof claim 82 and solvent.
 84. A thermosetting matrix made from thespin-on precursor of claim
 83. 85. A layer comprising the thermosettingmatrix of claim
 84. 86. The layer of claim 85, wherein the thermosettingmatrix is cured.
 87. The layer of claim 85, wherein the layer has adielectric constant of less than 2.7.
 88. The layer of claim 87, whereinthe layer has a dielectric constant of less than about 2.2.
 89. Thelayer of claim 85, wherein the layer has an average pore size diameterof less than about 20 nanometers.